CN112469755B

CN112469755B - Polyaziridine compounds

Info

Publication number: CN112469755B
Application number: CN201980048944.7A
Authority: CN
Inventors: 格拉达斯·可纳利斯·奥佛比克; 帕特里克·约翰内斯·玛丽亚·斯托尔斯; 达恩·范德兹瓦赫; 阿尔佛雷德·吉恩·保罗·布克曼
Original assignee: Kostron Netherlands Co ltd
Current assignee: Covestro Netherlands BV
Priority date: 2018-07-23
Filing date: 2019-07-17
Publication date: 2022-12-02
Anticipated expiration: 2039-07-17
Also published as: EP3827042B1; JP7271825B2; US11878969B2; EP3827042A1; AU2022201385A1; BR112021001004A2; WO2020020714A1; US20210332031A1; JP2021531242A; AU2022201385B2; CN112469755A; MX2021000699A; AU2019308863A1; US20240166634A1; AU2019308863B2

Abstract

The present invention relates to a polyaziridine compound having: a) 2 to 6 of the following structural units (a):

wherein R ', R', R ₁ 、R ₂ 、R ₃ And R ₄ As defined herein, m is an integer from 1 to 6; b) One or more linking chains, wherein each of these linking chains connects two of said building blocks a; and c) a molecular weight in the range of 600 daltons to 5000 daltons. The polyaziridine compounds may be used, for example, to crosslink carboxylic acid functional polymers, e.g., dissolved and/or dispersed in an aqueous medium.

Description

Polyaziridine compounds

The present invention relates to compounds having at least two aziridine groups (or aziridine groups), which may be used, for example, for crosslinking carboxylic acid functional polymers, for example, dissolved and/or dispersed in aqueous media.

Over the years, there has been an increasing demand for coatings with improved resistance (e.g., stain and solvent resistance), improved mechanical properties, and improved bond strength. One or more of these properties can be improved to a higher level by means of crosslinking. Many crosslinking mechanisms have been studied over the years and for aqueous dispersions the most useful crosslinking mechanisms include isocyanate crosslinking of hydroxyl functional dispersions, reaction between carbodiimides and carboxylic acids, epoxy crosslinking and crosslinking using aziridine based crosslinkers.

US-se:Sup>A-5133997 describes se:Sup>A coating composition comprising an aqueous dispersion of se:Sup>A linear aliphatic urethane resin, an anionic surfactant, and se:Sup>A crosslinker capable of promoting curing of the resin. Trimethylolpropane tris (2-methyl-1-aziridinepropionate), CAS No. 64265-57-2, is a polyfunctional aziridine crosslinking agent, is used as a crosslinking agent, is well known and has high activity for crosslinking carboxylic acid functional polymers. However, this cross-linking agent has unfavorable genotoxic characteristics. There is a need in the industry to improve the safety, health and environmental characteristics of adhesives, inks and coatings and the materials used to prepare them. Genotoxicity describes the nature of chemical or physical agents that cause any type of DNA damage that may not always result in a transmissible mutation. Mutagenicity refers to the induction of permanently transmissible DNA changes (as DNA components or chromosomal structures) that are maintained during somatic cell division and passed on to progeny in germ cells. Genotoxicity must not be confused with mutagenicity. All mutagens are genotoxic, and not all genotoxic material is mutagenic.

It is an object of the present invention to provide a compound having at least two aziridine groups, which has reduced genotoxicity compared to trimethylolpropane tris (2-methyl-1-aziridinepropionate). Compounds having at least two aziridine groups are also referred to herein as polyaziridine compounds.

Surprisingly, this object has been achieved by providing polyaziridine compounds having:

a) 2 to 6 of the following structural units (a):

wherein

R ₁ Is H;

R ₂ and R ₄ Independently selected from H, a linear group containing from 1 to 8 carbon atoms in the chain and optionally containing one or more heteroatoms, a branched or cyclic group containing from 3 to 8 carbon atoms in the chain and optionally containing one or more heteroatoms, phenyl, benzyl or pyridyl;

R ₃ is a linear group containing from 1 to 8 carbon atoms in the chain and optionally containing one or more heteroatoms, a branched or cyclic group containing from 3 to 8 carbon atoms in the chain and optionally containing one or more heteroatoms, a phenyl, benzyl or pyridyl group;

wherein R is ₂ And R ₃ (in R) ₂ In the case of being different from H) may be part of the same cyclic group containing from 3 to 8 carbon atoms;

r' = H or aliphatic hydrocarbon group containing 1 to 12 carbon atoms;

r "= H, aliphatic hydrocarbon group having 1 to 12 carbon atoms, alicyclic hydrocarbon group having 5 to 12 carbon atoms, aromatic hydrocarbon group having 6 to 12 carbon atoms, CH ₂ -O-(C＝O)-R”'、CH ₂ -O-R "" or CH ₂ -(OCR””'HCR””'H) _n -OR "" ", wherein R'" is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R "" is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms OR an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R "" is independently H OR an aliphatic hydrocarbon group containing 1 to 12 carbon atoms, and R "" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms;

wherein R' and R "may be part of the same saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms;

m is an integer of 1 to 6;

b) One or more linking chains (linking chains), wherein each of these linking chains connects two of the structural units a present in the polyaziridine compound; and

c) A molecular weight in the range of 600 daltons to 5000 daltons.

It has surprisingly been found that polyaziridine compounds according to the invention have reduced genotoxicity compared to trimethylolpropane tris (2-methyl-1-aziridinepropionate). The polyethylenimine compounds according to the invention show either only weakly positive induced genotoxicity or even they do not show genotoxicity, i.e. they show a level of genotoxicity which is comparable to the naturally occurring background.

Genotoxicity may be through as further described herein

The measurement is carried out by assay (Toxys, leiden, the Netherlands).

The assay can be applied to the pure substance or to the composition which is the direct product obtained in the preparation of the polyaziridine compound of the present invention. Positively induced genotoxicity refers to induction levels of the biomarkers Bscl2-GFP and Rtkn-GFP equal to or higher than 2-fold at least one of 10%, 25% and 50% cytotoxicity in the absence or presence of metabolic system rat S9 liver extract. Weakly positive induced genotoxicity refers to the induction levels of the biomarkers Bscl2-GFP and Rtkn-GFP being more than 1.5-fold and less than 2-fold (but less than 2-fold at 10%, 25% and 50% cytotoxicity) in the absence or presence of the metabolic system based on rat S9 liver extracts (aroclor 1254 induced rat, moltox, boone, NC, USA). By genotoxicity comparable to the naturally occurring background is meant that the induction levels of the biomarkers Bscl2-GFP and Rtkn-GFP are less than or equal to 10% in the absence and presence of the metabolic system based on rat S9 liver extracts (aroclor 1254-induced rat, boone, NC, USA),25% and 50% cytotoxicity. In the absence and presence of a metabolic system based on rat S9 liver extracts (aroclor 1254 induced rat, moltox, boone, NC, USA), the induction levels of the genotoxicity reporter genes Bscl2-GFP and Rtkn-GFP are preferably less than or equal to 1.5-fold at 10%, 25% and 50% cytotoxicity. Materials showing induction levels less than or equal to 1.5 times the induction level at 10%, 25% and 50% cytotoxicity in the absence and presence of a metabolic system based on rat S9 liver extract (aroclor 1254 induced rat, moltox, boone, NC, USA) are not genotoxic.

For all upper and/or lower bounds of any range given herein, unless specifically stated otherwise, the border values are included within the given range. Thus, when describing from x to y, it is meant to include x and y and also all intermediate values.

In this specification, the term "coating composition" encompasses paints, coatings, varnishes, adhesives and ink compositions, but is not limited to this list. The term "aliphatic hydrocarbon group" refers to optionally branched alkyl, alkenyl and alkynyl groups. The term "alicyclic hydrocarbon group" refers to cycloalkyl and cycloalkenyl groups optionally substituted with at least one aliphatic hydrocarbon group. The term "aromatic hydrocarbyl" refers to a benzene ring optionally substituted with at least one aliphatic hydrocarbyl group. These optionally substituted aliphatic hydrocarbon groups are preferably alkyl groups. Examples of alicyclic hydrocarbon groups having 7 carbon atoms are cycloheptyl and methyl-substituted cyclohexyl. An example of an aromatic hydrocarbon group having 7 carbon atoms is a methyl-substituted phenyl group. Examples of the aromatic hydrocarbon group having 8 carbon atoms are a xylyl group and an ethyl group-substituted phenyl group.

Although the structural units (A) present in the polyaziridine compounds according to the invention may independently have different R ₂ 、R ₃ 、R ₄ R ', R' and/or m, but the structural units (A) present in the polyaziridine compound are preferably identical to each other.

The polyaziridine compounds according to the invention are typically obtained as compositions in which, in addition to the polyaziridine compound, remaining starting materials, by-products and/or solvents for preparing the polyaziridine compound may be present. The composition may comprise only one polyaziridine compound according to the invention, but may also contain more than one polyaziridine compound according to the invention. For example, when mixtures of polyisocyanates are used as starting materials, mixtures of polyaziridine compounds are obtained.

The urethane aziridine compound of the present invention contains 2 to 6 structural units (a), preferably 2 to 4 structural units (a), more preferably 2 or 3 structural units (a).

R ₂ And R ₄ Independently selected from H; linear groups containing from 1 to 8 carbon atoms, optionally containing in the chain one or more heteroatoms, preferably selected from N, S and O; a branched or cyclic group containing carbon atoms of 3 to 8 carbon atoms and optionally containing in the chain one or more heteroatoms, preferably selected from N, S and O; a phenyl group; a benzyl group; or a pyridyl group. At R ₂ In the case of a difference from H, then R ₂ And R ₃ May be part of the same cyclic group containing 3 to 8 carbon atoms, preferably part of the same saturated alicyclic hydrocarbon group containing 3 to 8 carbon atoms. Preferably, R ₂ And R ₄ Independently selected from H, aliphatic hydrocarbon groups containing 1 to 8 carbon atoms or cycloaliphatic hydrocarbon groups containing 3 to 8 carbon atoms. More preferably, R ₂ And R ₄ Independently selected from H or aliphatic hydrocarbon groups containing 1 to 4 carbon atoms. More preferably, R ₂ And R ₄ Independently selected from H or aliphatic hydrocarbon groups containing 1 to 2 carbon atoms.

R ₃ Is a linear group containing from 1 to 8 carbon atoms and optionally containing one or more heteroatoms in the chain, preferably selected from N, S and O, a branched or cyclic group containing from 3 to 8 carbon atoms and optionally containing one or more heteroatoms in the chain, preferably selected from N, S and O, a phenyl, benzyl or pyridyl group. R ₃ Preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 8 carbon atoms, a phenyl group, a benzyl group or a pyridyl group. R is ₃ More preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In a preferred embodiment of the invention, R ₂ Is H, R ₃ Is C ₂ H ₅ And R is ₄ Is H. In another more preferred embodiment of the invention, R ₂ Is H, R ₃ Is CH ₃ And R is ₄ Is H or CH ₃ . In another even more preferred embodiment of the invention, R ₂ Is H, R ₃ Is CH ₃ And R is ₄ Is H.

m is an integer of 1 to 6, preferably m is 1 to 4, more preferably m is 1 or 2, and most preferably m is 1.

R' is H or an aliphatic hydrocarbon group containing 1 to 12 carbon atoms, preferably an alkyl group containing 1 to 12 carbon atoms. R' is preferably H or an alkyl group having 1 to 4 carbon atoms. More preferably, R' is H or an alkyl group containing 1 to 2 carbon atoms. Most preferably, R' is H.

R' is preferably H, an aliphatic hydrocarbon group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), an alicyclic hydrocarbon group having 5 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, CH ₂ -O-(C＝O)-R”'、CH ₂ -O-R "" or CH ₂ -(OCR””'HCR””'H) _n -OR "", wherein R '"is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R" "is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms OR an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, preferably 6 to 20, R" "is independently H OR methyl and R" "is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, OR R' and R" may be part of the same saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms. More preferably, R "= H, aliphatic hydrocarbon group containing 1 to 4 carbon atoms, CH ₂ -O-(C＝O)-R”'、CH ₂ -O-R "" or CH ₂ -(OCR””'HCR””'H) _n -OR "" wherein R' "is an alkyl group containing 1 to 12 carbon atoms and R" "is an alkyl group containing 1 to 12 carbon atoms, n is 1 to 35, R" "is independently H OR methyl, and R" "is an alkyl group containing 1 to 4 carbon atoms;

or R 'and R' may be part of the same saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms.

More preferably, R' is H and R "= alkyl containing 1 to 4 carbon atoms, CH ₂ -O-(C＝O)-R”'、CH ₂ -O-R "" or CH ₂ -(OCH ₂ CH ₂ ) _n -OCH ₃ Wherein R' "is preferably an alkyl group having 3 to 12 carbon atoms, more preferably a branched alkyl group having 3 to 12 carbon atoms, such as a neopentyl group or a neodecyl group. Most preferably, R' "is a branched C9 alkyl group. R "" is preferably an alkyl group having 1 to 12 carbon atoms. Non-limiting examples of R "" are ethyl, butyl, and 2-ethylhexyl.

The molecular weight of the polyaziridine compounds according to the invention is between 600 and 5000 daltons. The molecular weight of the polyethylenimine compounds according to the invention is preferably at most 3800 dalton, more preferably at most 3600 dalton, more preferably at most 3000 dalton, more preferably at most 1600 dalton, even more preferably at most 1200 dalton. The molecular weight of the polyethylenimine compounds according to the invention is preferably at least 700 dalton, more preferably at least 800 dalton, even more preferably at least 840 dalton and most preferably at least 1000 dalton. As used herein, the molecular weight of the polyethylenimine compound is the calculated molecular weight. The calculated molecular weight is obtained by adding the atomic masses of all the atoms present in the structural formula of the polyethylenimine compound. If a polyaziridine compound is present in a composition comprising more than one polyaziridine compound according to the present invention, for example when one or more of the starting materials used to prepare the polyaziridine compound is a mixture, a molecular weight calculation may be performed for each compound present alone in the composition. As described in the experimental section below, MALDI-TOF mass spectrometry can be used to measure the molecular weight of the polyethylenimine compounds according to the present invention.

The polyaziridine compounds according to the present invention comprise one or more linking chains, wherein each of these linking chains connects two of the structural units a. The linking chain present in the polyaziridine compound preferably consists of 2 to 300 atoms, more preferably 5 to 250 atoms, most preferably 6 to 100 atoms. The atoms of the connecting chain are preferably C, N, O, S and/or P, preferably C, N and/or O.

The connecting chain is defined as the shortest chain of consecutive atoms connecting two building blocks a. The lower diagram shows an example of a polyaziridine compound according to the invention, the linking chain between two structural units a.

Any two of the structural units a present in the polyaziridine compounds of the present invention are connected by a connecting chain as defined herein. Thus, each structural unit a present in the polyaziridine compounds of the present invention is linked to each other structural unit a by a linking chain as defined herein. In the case of the polyaziridine compounds according to the invention having two structural units a, the polyaziridine compound has one such connecting chain connecting the two structural units. In the case where the polyaziridine compound according to the present invention has three structural units a, the polyaziridine compound has three linking chains, wherein each of the three linking chains links structural unit a with another structural unit a, i.e., a first structural unit a is linked with a second structural unit a by a linking chain, and both the first and second structural units a are independently linked with a third structural unit a by their respective linking chains.

The following figures show examples of polyaziridine compounds having three structural units a, three linking chains, where each linking chain connects two structural units a.

The polyaziridine compounds according to the invention having more than two structural units a have a number of connecting chains according to the following equation: LC = (AN-1) × AN) }/2, where LC = number of connecting chains in the polyethylenimine compound and AN = number of structural units a in the polyethylenimine compound. Thus, for example, if there are 5 structural units a in the polyaziridine compound, AN =5; this means that there are { (5-1) × 5}/2=10 connecting chains.

Preferably, the number of consecutive C atoms and optionally O atoms between the N atom of a carbamate group in structural unit a and another N atom (which is present in the linking chain or is an N atom of a carbamate group of another structural unit a) is at most 9, as shown for example in the polyaziridine compound according to the invention below.

The polyaziridine compound according to the present invention preferably comprises one or more linking groups (connecting groups), wherein each of these linking groups connects two of the structural units a, wherein a linking group is defined as an array of consecutive functional groups (as defined herein) connecting two structural units a. In the present invention, the linking group preferably consists of at least one functional group selected from the group consisting of: an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, an ether functional group, an ester functional group, an amide functional group, a carbonate functional group, a carbamate functional group, a urea functional group, a biuret functional group, an allophanate functional group, a uretdione functional group, and any combination thereof.

The following figure shows in bold an exemplary linking group of a polyaziridine compound according to the present invention. In this example, the linking group linking two of the structural units a consists of the following array of consecutive functional groups: aliphatic Hydrocarbon functional group 1 (straight chain C) ₆ H ₁₂ ) Isocyanurate 2 (Cyclic C) ₃ N ₃ O ₃ ) Functional groups and aliphatic Hydrocarbon function 3 (straight chain C) ₆ H ₁₂ )。

The following figures show in bold the following exemplary linking groups of the polyaziridine compounds according to the invention. In this example, the linking group connecting the two structural units a consists of the following array of consecutive functional groups: aliphatic Hydrocarbon functional group 1 (straight chain C) ₆ H ₁₂ ) Isocyanurate 2 (Cyclic C) ₃ N ₃ O ₃ ) And aliphatic Hydrocarbon function 3 (straight chain C) ₆ H ₁₂ )。

Any two of the structural units a present in the polyaziridine compounds of the present invention are connected by a linking group as defined herein. Thus, each structural unit a present in the polyaziridine compounds of the present invention is linked to each other structural unit a using a linking group as defined in the present invention. In the case of the polyaziridine compounds according to the invention having two structural units a, the polyaziridine compound has one such linking group connecting the two structural units. In the case of a polyaziridine compound according to the invention having three structural units a, the polyaziridine compound has three such linking groups, wherein each of the three linking groups links structural unit a with another structural unit a.

The following figure shows three linking groups for an example of a polyaziridine compound having three structural units a, wherein each linking group of the three linking groups connects two structural units a. One linking group consists of the following array of consecutive functional groups: aliphatic Hydrocarbon function 1 (straight chain C) linking building blocks A marked A1 and A2 ₆ H ₁₂ ) Isocyanurate 2 (Cyclic C) ₃ N ₃ O ₃ ) And aliphatic Hydrocarbon function 3 (straight chain C) ₆ H ₁₂ ). For the connection between the building blocks A marked A1 and A3, the connectionThe group consists of an array of consecutive functional groups: aliphatic Hydrocarbon Functions 1 (straight chain C) ₆ H ₁₂ ) Isocyanurate 2 (Cyclic C) ₃ N ₃ O ₃ ) And aliphatic Hydrocarbon function 4 (straight chain C) ₆ H ₁₂ ) Whereas for the linkage between building blocks a, labeled A2 and A3, the linking group consists of an array of consecutive functional groups: aliphatic Hydrocarbon functional group 3 (straight chain C) ₆ H ₁₂ ) Isocyanurate 2 (Cyclic C) ₃ N ₃ O ₃ ) And aliphatic Hydrocarbon functional group 4 (straight chain C) ₆ H ₁₂ )。

The lower diagram shows another example of a polyaziridine compound according to the invention, with a linking chain between two structural units a.

In this example, the linking group connecting the two structural units a consists of the following array of consecutive functional groups: aliphatic Hydrocarbon function 1 (branched C) ₃ H ₆ ) Aromatic hydrocarbon function 2 (benzene ring) and aliphatic hydrocarbon function 3 (branched C) ₃ H ₆ )。

In another example of the polyaziridine compound according to the invention, the linking group connecting two structural units a consists of an array of consecutive functional groups: aliphatic Hydrocarbon Functions 1 (straight chain C) ₆ H ₁₂ ) Uretdione 2 (Cyclic C) ₂ N ₂ O ₂ ) And aliphaticHydrocarbon function 3 (straight-chain C) ₆ H ₁₂ )。

Preferably, the linking group consists of at least one functional group selected from the group consisting of: aliphatic hydrocarbon functional groups (preferably containing from 1 to 8 carbon atoms), cycloaliphatic hydrocarbon functional groups (preferably containing from 4 to 10 carbon atoms), aromatic hydrocarbon functional groups (preferably containing from 6 to 12 carbon atoms), isocyanurate functional groups, iminooxadiazinedione functional groups, carbamate functional groups, urea functional groups, biuret functional groups, and any combination thereof. The linking group preferably contains an isocyanurate, iminooxadiazinedione, biuret, allophanate or uretdione functional group. More preferably, the linking group contains an isocyanurate functional group or an iminooxadiazinedione functional group. For clarity, the polyaziridine compound may be obtained from the reaction product of one or more suitable compounds B with a hybrid isocyanurate (e.g., HDI/IPDI isocyanurate), thereby producing a polyaziridine compound having a linking group consisting of an array of consecutive functional groups: straight chain C ₆ H ₁₂ (i.e. an aliphatic hydrocarbon function having 6 carbon atoms), isocyanurate function (cyclic C) ₃ N ₃ O ₃ ) And

(i.e., an alicyclic hydrocarbon functionality having 9 carbon atoms and an aliphatic hydrocarbon functionality having 1 carbon atom).

The term "aliphatic hydrocarbon functionality" refers to optionally branched alkyl, alkenyl and alkynyl groups. Although optional branches of C atoms are part of the linking group, they are not part of the linking chain. The term "cycloaliphatic hydrocarbon functionality" refers to cycloalkyl and cycloalkenyl groups optionally substituted with at least one aliphatic hydrocarbon group. Although the optional aliphatic hydrocarbyl substituents are part of the linking group, they are not part of the linking chain. The term "aromatic hydrocarbon functionality" refers to a benzene ring optionally substituted with at least one aliphatic hydrocarbon group. The optionally substituted aliphatic hydrocarbon group is preferably an alkyl group. Although the optional aliphatic hydrocarbyl substituents are part of the linking group, they are not part of the linking chain.

On the linking group, one or more substituents may be present as pendant groups on the linking group, as shown in bold, for example, in the polyaziridine compounds below. These side groups are not part of the linking group.

The aziridinyl group has the following structural formula:

isocyanurate functionality is defined as

Iminooxadiazinedione (iminooxadiazinedione) functional groups are defined as

Allophanate functions are defined as

Uretidione functionality is defined as

Biuret functional groups are defined as

In a preferred embodiment of the present invention, the linking group present in the polyaziridine compound of the present invention consists of the following functional groups: at least one aliphatic hydrocarbon function and/or at least one alicyclic hydrocarbon function and optionally at least one aromatic hydrocarbon function and optionally an isocyanurate function or an iminooxadiazinedione function or an allophanate function or a uretidione function. Preferably, the linking group present in the polyaziridine compound of the present invention consists of the following functional groups: at least one aliphatic hydrocarbon function and/or at least one cycloaliphatic hydrocarbon function and optionally at least one aromatic hydrocarbon function and optionally an isocyanurate function or an iminooxadiazinedione function. A very suitable way to obtain such polyaziridine compounds is to react a compound B having the following structural formula with an aliphatically reactive polyisocyanate:

the term "polyisocyanate having aliphatic reactivity" refers to a compound in which all isocyanate groups are directly bonded to an aliphatic or alicyclic hydrocarbon group, regardless of whether an aromatic hydrocarbon group is also present. The polyisocyanate having aliphatic reactivity may be a mixture of polyisocyanates having aliphatic reactivity. The tendency of compounds based on polyisocyanates having aliphatic reactivity to yellow over time is reduced when compared with similar compounds based on polyisocyanates having aromatic reactivity. The term "polyisocyanate having aromatic reactivity" refers to a compound in which all isocyanate groups are directly bonded to an aromatic hydrocarbon group, regardless of whether an aliphatic or alicyclic group is also present. Preferred polyisocyanates with aliphatic reactivity are 1, 5-pentamethylene diisocyanate PDI, 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 4' -dicyclohexylmethane diisocyanate H12MDI, 2, 4-trimethylhexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate TMXDI (all isomers) and higher molecular weight variants, such as for example their isocyanurates or iminooxadiazinediones. In this embodiment, preferably, the linking group consists of an array of consecutive functional groups: aliphatic, aromatic, and aliphatic hydrocarbon functionalities (e.g., when TMXDI is used to make polyaziridine compounds), or the linking group consists of an array of consecutive functional groups: alicyclic hydrocarbon functional groups, aliphatic hydrocarbon functional groups, and alicyclic hydrocarbon functional groups (e.g., when H12MDI is used to make polyaziridine compounds), or more preferably, the linking group consists of an array of consecutive functional groups: an aliphatic hydrocarbon functional group, an isocyanurate functional group or an iminooxadiazinedione functional group, and an aliphatic hydrocarbon functional group. Most preferably, in this embodiment, the linking group consists of an array of consecutive functional groups: aliphatic hydrocarbon functional groups, isocyanurate functional groups, and aliphatic hydrocarbon functional groups (e.g., when the polyaziridine compound is prepared using the isocyanurate of 1, 6-hexamethylene diisocyanate and/or the isocyanurate of 1, 5-pentamethylene diisocyanate).

In another embodiment of the present invention, the polyaziridine compound according to the present invention is according to the following structural formula:

wherein Z is the molecular residue obtained by removing the isocyanate-reactive group XH of the molecule;

q is an integer of 2 to 6;

i is the index of the different groups D and is an integer from 1 to q;

D _i independently have the formula

Wherein X is NR ₁₁ S or O, wherein R ₁₁ Is H or alkyl having 1 to 4 carbon atoms;

y is an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a combination thereof;

j is an integer from 1 to p;

p is an integer of 0 to 10.

m、R'、R”、R ₁ 、R ₂ 、R ₃ And R ₄ As defined above. In this embodiment of the invention, the polyaziridine compound contains 2 to 6D _i A group. Albeit structural element D _i May independently be the same or different, but the structural unit D _i Preferably identical to each other.

Isocyanate-reactive groups XH are defined herein as hydroxyl (X is O), primary amine (X is NH) or secondary amine (X is NR) ₁₁ Wherein R is ₁₁ Alkyl having 1 to 4 carbon atoms) or a thiol (X is S). Preferred isocyanate-reactive groups XH are hydroxyl (X is O), primary amine (X is NH) or secondary amine (X is NR) ₁₁ Wherein R is ₁₁ An alkyl group having 1 to 4 carbon atoms). More preferred isocyanate-reactive groups XH are hydroxyl groups (X is O) and primary amines (X is NH). The molecule from which the isocyanate-reactive group is removed to obtain Z is preferably a diol, triol, polyether having terminal isocyanate-reactive groups, polyamide having terminal isocyanate-reactive groups, polycarbonate having terminal isocyanate-reactive groups, or polysiloxane having terminal isocyanate-reactive groups, the terminal isocyanate-reactive groups in the polysiloxane having terminal isocyanate-reactive groups being linked to the siloxane by at least one carbon atom. In the case where Z is a molecular residue obtained by removing an isocyanate-reactive group XH of a diol or triol, the isocyanate-reactive group XH is a hydroxyl group and thus X is O. In the case where Z is a molecular residue obtained by removing the isocyanate-reactive group XH of the polyether having a terminal isocyanate-reactive group or the polyamide having a terminal isocyanate-reactive group, the isocyanate-reactive group XH is preferably NH2 (hence X is NH) or OH (hence X is O), and more preferably X is OThe isocyanate-reactive group XH is OH (thus X is O). In case Z is a molecular residue obtained by removing the isocyanate reactive groups XH of the polycarbonate having terminal isocyanate reactive groups, the isocyanate reactive groups are preferably OH and thus X is O.

In the case where j is greater than 1, then Z may be the same or different.

Preferably, q is 2 or 3, and more preferably, q is 1.

Preferably, p is an integer from 0 to 10, more preferably from 0 to 5, most preferably from 0 to 3.

In this embodiment, for all D _i P is most preferably 0, and thus D _i Independently have the structural formula (I) as follows,

wherein m, R', R ₁ 、R ₂ 、R ₃ And R ₄ As defined above. Preferably m is 1.

Albeit of structural unit D _i May independently be the same or different, but structural unit D _i Preferably identical to each other.

The total amount of cyclic structures (other than aziridine) present in the polyaziridine compound is preferably at most 3, as this results in a lower viscosity than when higher amounts of cyclic structures are present. Lower viscosities are easier to handle and/or require less co-solvent to make the compound easier to handle. Polyaziridine compounds having more than three ring structures may cause more difficulty when dissolving such polyaziridines if the polyaziridine compound is solid at ambient temperature. The total amount of cyclic structures (other than aziridines) present in the polyaziridine compound is more preferably 0 to 2, even more preferably 1 or 2, and most preferably 1, which is preferably an isocyanurate or iminooxadiazinedione.

The polyaziridine compound according to the present invention preferably contains at least 5 wt.%, more preferably at least 5.5 wt.%, more preferably at least 6 wt.%, more preferably at least 9 wt.%, more preferably at least 12 wt.% and preferably less than 25 wt.%, preferably less than 20 wt.% urethane linkages. The aziridine equivalent weight of the polyethylenimine compounds according to the invention (molecular weight of the polyethylenimine compound divided by the number of aziridine groups present in the polyethylenimine compound) is preferably at least 200 dalton, more preferably at least 230 dalton and even more preferably at least 260 dalton, and preferably at most 2500 dalton, more preferably at most 1000 dalton and even more preferably at most 500 dalton.

If desired, the polyaziridine compound may be stabilized with 0.1% to 1% by weight of a tertiary amine, preferably a beta-hydroxylamine (e.g., amietol M21 or Amietol M-12).

The polyaziridine compounds according to the invention are preferably obtained by reacting at least a polyisocyanate with a compound B having the following structural formula:

wherein the molar ratio of compound B to polyisocyanate is from 2 to 6, more preferably from 2 to 4, and most preferably from 2 to 3, and wherein m, R', R ", R ″ ₁ 、R ₂ 、R ₃ And R ₄ As defined above. The reaction of the polyisocyanate with the compound B can be carried out by: the equivalent amount of polyisocyanate is contacted with compound B in the presence of, for example, a tin catalyst (e.g. dibutyltin laurate) or a bismuth catalyst (e.g. bismuth neodecanoate) at a temperature in the range from 0 ℃ to 110 ℃, more suitably from 20 ℃ to 110 ℃, more suitably from 40 ℃ to 95 ℃, even more suitably from 60 ℃ to 85 ℃. Solvents such as dimethylformamide DMF, acetone and/or methyl ethyl ketone may be used. The polyisocyanate contains at least 2 isocyanate groups, preferably an average of at least 2.5 isocyanate groups, more preferably an average of at least 2.8 isocyanate groups. Mixtures of polyisocyanates can also be used as starting materials. Preferred polyisocyanates are those that are aliphatic reactive. The term "polyisocyanate having aliphatic reactivity" means thatIn which all isocyanate groups are directly bonded to an aliphatic or alicyclic hydrocarbon group, irrespective of whether an aromatic hydrocarbon group is also present. The polyisocyanate having aliphatic reactivity may be a mixture of polyisocyanates having aliphatic reactivity. Preferred polyisocyanates with aliphatic reactivity are 1, 5-pentamethylene diisocyanate PDI, 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 4' -dicyclohexylmethane diisocyanate H12MDI, 2, 4-trimethylhexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, p-tetramethylxylene diisocyanate (p-TMXDI) and its meta-isomers, and also higher molecular weight variants thereof, for example their isocyanurates or iminooxadiazinediones or allophanates or uretdiones. More preferred aliphatic reactive polyisocyanates are 4,4' -dicyclohexylmethane diisocyanate H12MDI, m-TMXDI, the isocyanurate of 1, 6-hexamethylene diisocyanate or iminooxadiazinedione or allophanate or uretdione and the isocyanurate of 1, 5-pentamethylene diisocyanate. Suitable HDI-containing iminooxadiazinedione trimers are those obtainable from Covestro

N3900. Suitable HDI-containing allophanates are available from Covestro

XP2860. Suitable HDI-containing uretdiones are those available from Covestro

And N3400. Suitable HDI-based isocyanurate trimers can be obtained, for example, from Covestro (R) ((R))

N3600)、Vencorex(Tolonate ^TM HDT LV)、Asahi Kasei(Duranate ^TM TPA-100)、Evonik(

HT 2500/LV) and Tosoh (

HXR LV). Methods for preparing compound (B) and derivatives are known in the art. For example, s.lesniak, m.rachwalski, s.jarzynski, e.obijalska Tetrahedron asymm.2013,24 1336-1340 describe the synthesis of 1- (2-methylazidin-1-yl) propan-2-ol. A.Baklien, M.V.Leeding, J.Kolm Aust.J.chem.1968,21,1557-1570 describes the synthesis of 1- (aziridin-1-yl) propan-2-ol. Preferred aziridine compounds for preparing compound B are propyleneimine and ethylenimine. The synthesis of ethyl aziridine is described, for example, in EP0227461B 1. The most preferred aziridine compound for preparing compound B is propyleneimine.

Compound B is preferably obtained by reacting at least a non-OH functional monoepoxide compound with an aziridine compound having the following structural formula (C):

wherein R is ₁ 、R ₂ 、R ₃ And R ₄ As defined above. The non-OH functional monoepoxide can be a mixture of different non-OH functional monoepoxides. Non-limiting examples of non-OH-functional monoepoxides are ethylene oxide, propylene oxide, 2-ethylethylene oxide, n-butylglycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, 4-tert-butylphenyl 2, 3-epoxypropyl ether (= tert-butylphenyl glycidyl ether), cresol glycidyl ether (ortho-or para-position), and glycidyl neodecanoate. The non-OH-functional monoepoxide is preferably selected from the group consisting of: ethylene oxide (CAS No. 75-21-8), propylene oxide (CAS No. 75-56-9), 2-ethylethylene oxide (CAS No. 106-88-7), n-butyl glycidyl ether (CAS No. 2426-08-6), 2-ethylhexyl glycidyl ether (CAS No. 2461-15-6), glycidyl neodecanoate (CAS No. 26761-45-5), and any mixtures thereof. More preferably, the non-OH functional monoepoxide is selected from the group consisting ofGroup of items: propylene oxide (CAS No. 75-56-9), 2-ethylethylene oxide (CAS No. 106-88-7), n-butyl glycidyl ether (CAS No. 2426-08-6), 2-ethylhexyl glycidyl ether (CAS No. 2461-15-6), glycidyl neodecanoate (CAS No. 26761-45-5), and any mixtures thereof.

The polyaziridine compounds according to the invention are preferably obtained in a process comprising at least the following steps (i) and (ii):

(i) Reacting an aziridine having the formula (C) with an at least non-OH-functional monoepoxide compound to obtain compound B, and

(ii) Reacting compound B with a polyisocyanate.

Step (i) may be carried out, for example, by contacting one equivalent of the epoxide compound with one equivalent of aziridine at atmospheric pressure at a temperature in the range from 20 ℃ to 110 ℃, more suitably from 40 ℃ to 95 ℃, even more suitably from 60 ℃ to 85 ℃. The reaction of the adduct obtained in step (i) (compound (B)) with a polyisocyanate (step (ii)) can be carried out, for example, by: the equivalent amount of polyisocyanate is contacted with the adduct in the presence of, for example, a tin catalyst (e.g., dibutyltin laurate) at atmospheric pressure at a temperature in the range of from 20 ℃ to 110 ℃, more suitably from 40 ℃ to 95 ℃.

In a preferred embodiment, the polyethylenimine compounds according to the invention preferably contain polyoxyethylene (-O-CH 2-CH 2-) in an amount of preferably at least 0.1 wt.%, more preferably at least 6 wt.%, more preferably at least 10 wt.% and preferably less than 45 wt.%, more preferably less than 25 wt.%, most preferably less than 16 wt.%, relative to the polyethylenimine compound _x Radical, polyoxypropylene (-O-CHCH 3-CH 2-) _x Radicals and/or polytetrahydrofuran (-O-CH 2-CH 2) _x A group. Preferably, the polyethylenimine compound contains polyoxyethylene (-O-CH 2-CH 2-) in an amount of preferably at least 0.1 wt.%, more preferably at least 6 wt.%, more preferably at least 10 wt.% and preferably in an amount of less than 45 wt.%, more preferably less than 25 wt.% and most preferably less than 16 wt.% relative to the polyethylenimine compound _x A group. For the sake of clarity, it should be noted thatIn the case where R '= H and R "= H or in the case where R' = H and R" = CH ₃ In the case of (a), one oxyethylene group or respectively one oxypropylene group is present in the structural unit (a) and is then included in the preferred amount of oxyethylene or oxypropylene group as defined herein. Contains polyoxyethylene (-O-CH 2-CH 2-) _x The polyaziridine compound of the group is preferably the reaction product of at least compound (B), a polyisocyanate and an alkoxy poly (ethylene glycol), preferably methoxy poly (ethylene glycol) (MPEG), and/or poly (ethylene glycol). The reaction product may be obtained by reacting at least compound (B), a polyisocyanate and an alkoxy poly (ethylene glycol) and/or a poly (ethylene glycol). The reaction product may also be obtained by reacting a polyisocyanate with an alkoxy poly (ethylene glycol) and/or poly (ethylene glycol) and reacting the compound thus obtained with compound (B). The reaction product may also be obtained by reacting compound (B) with a polyisocyanate and reacting the compound thus obtained with an alkoxy poly (ethylene glycol) and/or poly (ethylene glycol).

Number average molecular weight M in the polyaziridine compound as defined above _n Above 2200 daltons, preferably M _n The amount of alkoxy poly (ethylene glycol) (preferably methoxy poly (ethylene glycol) (MPEG)) and/or poly (ethylene glycol) (PEG) chains above 1600 daltons is preferably less than 35 wt%, more preferably less than 15 wt%, more preferably less than 5 wt% and most preferably 0 wt%. M of methoxy poly (ethylene glycol) (MPEG) and/or poly (ethylene glycol) (PEG) chains present in polyaziridine compounds _n Preferably below 1100 daltons, more preferably below 770 daltons and most preferably below 570 daltons.

Examples of preferred polyaziridine compounds according to the invention are

And

another aspect of the present invention is a crosslinker composition comprising at least one polyaziridine compound as defined above, and further comprising at least one additional component, such as a solvent, remaining starting materials and/or by-products, for preparing the polyaziridine compound according to the present invention. The crosslinker composition may comprise only one polyaziridine compound according to the invention, but may also contain more than one polyaziridine compound according to the invention. For example, when mixtures of polyisocyanates are used as starting materials for preparing polyaziridines, mixtures of polyaziridine compounds are obtained. After the polyaziridine compound according to the invention has been obtained, the polyaziridine compound according to the invention may be isolated, the reaction product may be used without further purification, or the solvent used to prepare the polyaziridine compound may be removed from the composition obtained in the preparation of the polyaziridine compound of the invention. The amount of polyethylenimine compound according to the present invention in the crosslinker composition is typically at least 10 wt.%, often at least 15 wt.% and most typically at least 25 wt.%, relative to the total amount of the composition. The amount of polyaziridine compound according to the present invention in the crosslinker composition is preferably at least 60 wt.%, more preferably at least 80 wt.%, and most preferably at least 99 wt.%, relative to the total amount of the crosslinker composition. The molecular weight of the polyethylenimine compound in the crosslinker composition is in the range of 600 daltons to 5000 daltons. Preferred molecular weights are as described above, and the molecular weight of the polyethylenimine compound is determined using MALDI-TOF-MS as described in the experimental section below. MALDI-TOF-MS refers to matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

The amount of aziridine functional molecules present in the crosslinker composition according to the invention is preferably below 5 wt.%, more preferably below 2 wt.%, more preferably below 1 wt.%, more preferably below 0.5 wt.% and most preferably below 0.1 wt.%, relative to the total weight of the crosslinker composition, of aziridine functional molecules having a molecular weight of below 250 dalton, more preferably below 350 dalton, even more preferably below 450 dalton, even more preferably below 550 dalton and even more preferably below 580 dalton, wherein the molecular weight is determined using LC-MS as described in the experimental section below.

The average number of aziridinyl groups per aziridinyl group-containing molecule in the composition is preferably at least 1.8, more preferably at least 2, more preferably at least 2.2 and preferably less than 10, more preferably less than 6 and most preferably less than 4. Most preferably, the average number of aziridinyl groups per aziridinyl group containing molecule in the composition is from 2.2 to 3. The calculated average amount of urethane bonds relative to the total weight of the polyaziridine compound according to the present invention present in the crosslinker composition is at least 5 wt.%, more preferably at least 5.5 wt.%, more preferably at least 6 wt.%, more preferably at least 9 wt.%, more preferably at least 12 wt.%, and preferably less than 25 wt.%, preferably less than 20 wt.%.

In view of the potential water-sensitivity of the polyaziridine compounds according to the present invention, the crosslinker composition preferably does not contain a significant amount of water, and more preferably does not contain water. By free of significant amounts of water is meant less than 15 wt%, preferably less than 5 wt%, more preferably less than 1 wt% and most preferably less than 0.1 wt%. In view of the potential water sensitivity of the polyaziridine compounds according to the present invention, water is preferably not deliberately added to the composition (i.e., a small amount of water may be present in the compound used to prepare the polyaziridine compound according to the present invention).

The polyethylenimine compound according to the invention preferably has a brookfield viscosity at 25 ℃ of at least 500mpa.s, more preferably at least 1200mpa.s, more preferably at least 3000mpa.s, and a brookfield viscosity at 25 ℃ of preferably at most 1000000mpa.s, more preferably at most 100000mpa.s, more preferably at most 30000mpa.s, more preferably at most 10000mpa.s and most preferably 5000mpa.s. As used herein, brookfield viscosity is determined according to ISO 2555-89. In an alternative embodiment, the viscosity of polyethylenimine is measured in 20% Dimethylformamide (DMF) at 80% solids with a Brookfield with spindle S63 at 25 ℃. The viscosity as measured according to this method is preferably in the range of 300mpa.s to 20000mpa.s, more preferably in the range of 500mpa.s to 12000mpa.s, and most preferably in the range of 700mpa.s to 3000 mpa.s.

The polyaziridine compound or crosslinker composition comprising at least one polyaziridine compound as defined above according to the invention may advantageously be used as a crosslinker to crosslink carboxylic acid functional polymers, preferably carboxylic acid functional polymers dissolved and/or dispersed in an aqueous medium.

Another aspect of the present invention is a two-component system comprising a first component and a second component which are separate and distinct from each other, wherein the first component comprises a carboxylic acid functional polymer dissolved and/or dispersed in an aqueous medium, and wherein the second composition comprises a polyaziridine compound as defined above or a crosslinker composition comprising at least one polyaziridine compound as defined above, wherein the first component and the second component are stored separately, in that the crosslinking reaction between the crosslinker and the polymer to be crosslinked can start immediately after mixing the crosslinker with the aqueous composition of the polymer to be crosslinked. Non-limiting examples of crosslinkable carboxylic acid functional polymers are vinyl polymers (such as styrene-acrylic acid), (meth) acrylic acid copolymers, vinyl acetate (co) polymers (such as vinyl acetate vinyl chloride ethylene polymers), polyurethanes, condensation polymers (such as polyesters, polyamides, polycarbonates), and hybrids of any of these polymers, wherein at least one of the two polymers has carboxylic acid functional groups. The invention also relates to a coating composition obtained by: mixing the first and second components of the two-component system immediately prior to application of the coating composition, wherein the coating composition comprises aziridinyl groups Q and carboxylic acid groups in amounts such that the Stoichiometric Amount (SA) of aziridinyl groups Q on the carboxylic acid groups is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.5, even more preferably from 0.25 to 0.95, most preferably from 0.3 to 0.8.

The invention also relates to a substrate having a coating obtained by: (i) Applying a coating composition as described above to the substrate, and (ii) drying the coating composition by evaporating volatiles. Drying of the coating composition is preferably carried out at a temperature below 160 ℃, preferably below 90 ℃, more preferably below 50 ℃ and most preferably at ambient temperature. The coating composition according to the invention can be applied to any kind of substrate, such as wood, leather, concrete, textiles, plastics, vinyl flooring, glass, metal, ceramics, paper, wood-plastic composites, glass fibre reinforcement. The thickness of the dry coating on the substrate is preferably from 1 micron to 200 microns, more preferably from 5 microns to 150 microns, most preferably from 15 microns to 90 microns. Where the coating composition is an ink composition, the thickness of the dry ink is preferably from 0.005 micron to 35 micron, more preferably from 0.05 micron to 25 micron, most preferably from 4 micron to 15 micron.

The invention is further defined by a set of exemplary embodiments as set forth below. Any of the embodiments, aspects and preferred features or ranges as disclosed in the present application may be combined in any combination, unless otherwise indicated herein or if clearly not technically feasible to the skilled person.

[1] A polyaziridine compound, wherein the polyaziridine has 2 to 6 of the following structural units (a):

wherein

R ₁ Is H;

R ₂ and R ₄ Independently selected from H, a linear group containing from 1 to 8 carbon atoms and optionally containing one or more heteroatoms (preferably selected from N, S, O), a branched or cyclic group containing from 3 to 8 carbon atoms and optionally containing one or more heteroatoms (preferably selected from N, S, O), phenyl, benzyl or pyridyl;

R ₃ is a compound containing 1 to 8 carbon atoms and optionally one or more heteroatoms (preferably selected from N, S, O)) A linear group of (a), an alicyclic hydrocarbon group having 3 to 8 carbon atoms, a phenyl group, a benzyl group or a pyridyl group;

wherein R is ₂ And R ₃ (in R) ₂ In the case where it is different from H) may be part of the same cyclic group containing 3 to 8 carbon atoms;

r' = H or aliphatic hydrocarbon group containing 1 to 12 carbon atoms;

r "= H, aliphatic hydrocarbon group having 1 to 12 carbon atoms, alicyclic hydrocarbon group having 5 to 12 carbon atoms, aromatic hydrocarbon group having 6 to 12 carbon atoms, CH ₂ -O-(C＝O)-R”'、CH ₂ -O-R "" or CH ₂ -(OCR””'HCR””'H) _n -OR "" ", wherein R '" is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R "" is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms OR an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R ""' is independently H OR an aliphatic hydrocarbon group containing 1 to 12 carbon atoms, and R "" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms;

m is an integer of 1 to 6;

the polyaziridine compound further comprises one or more linking chains, wherein each of these linking chains connects two of the structural units a present in the polyaziridine compound, wherein the linking chain preferably consists of 2 to 300 atoms, more preferably consists of 5 to 250 atoms, most preferably consists of 6 to 100 atoms; and is provided with

Wherein the molecular weight of the polyethylenimine compound is in the range of 600 daltons to 5000 daltons, wherein the molecular weight of the polyethylenimine compound is calculated or measured using MALDI-TOF mass spectrometry as described in the experimental section below.

[2] The polyaziridine compound according to embodiment [1], wherein the polyaziridine compound contains 2 to 4 structural units (a), preferably 2 or 3 structural units (a), wherein the structural units (a) present in the polyaziridine compound are preferably identical to each other.

[3]According to embodiment [1]Or [2]]The polyaziridine compound, wherein R ₂ And R ₄ Independently selected from H or aliphatic hydrocarbon radicals containing 1 to 8 carbon atoms, preferably R ₂ And R ₄ Independently selected from H or aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms, preferably R ₂ And R ₄ Independently selected from H or an aliphatic hydrocarbon group containing 1 to 2 carbon atoms.

[4]According to [1]To [ 3]]The polyaziridine compound of any embodiment of (1), wherein R ₃ Is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably R ₃ Is an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[5]According to [1]To [ 4]]The polyaziridine compound of any embodiment of (1), wherein R ₂ Is H, R ₃ Is C ₂ H ₅ And R is ₄ Is H.

[6]According to [1]]To [ 4]]The polyaziridine compound of any embodiment of (1), wherein R ₂ Is H, R ₃ Is CH ₃ And R is ₄ Is H.

[7]According to [1]To [ 4]]The polyaziridine compound of any embodiment of (1), wherein R ₂ Is H, R ₃ Is CH ₃ And R is ₄ Is CH ₃ 。

[8] The polyaziridine compound according to any of embodiments [1] to [7], wherein m is 1.

[9] The polyaziridine compound according to any of embodiments [1] to [8], wherein R ' is H or an alkyl group containing 1 to 12 carbon atoms, preferably R ' is H or an alkyl group containing 1 to 4 carbon atoms, more preferably R ' is H or an alkyl group containing 1 to 2 carbon atoms.

[10]According to [1]To [9]]The polyaziridine compound of any embodiment in (1), wherein R "is H, an aliphatic hydrocarbon group containing 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), an alicyclic hydrocarbon group containing 5 to 12 carbon atoms, an aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH ₂ -O-(C＝O)-R”'、CH ₂ -O-R "" or CH ₂ -(OCR””'HCR””'H) _n -OR "" wherein R "'Is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R "" is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms or an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, preferably 6 to 20, R "" is independently H or methyl and R "" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, or R' and R "may be part of the same saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms. More preferably, R' is H and R "= alkyl containing 1 to 4 carbon atoms, CH ₂ -O-(C＝O)-R”'、CH ₂ -O-R "" or CH ₂ -(OCH ₂ CH ₂ ) _n -OCH ₃ Wherein R '"is preferably an alkyl group containing 3 to 12 carbon atoms, more preferably a branched alkyl group having 3 to 12 carbon atoms, most preferably R'" is a branched C9 alkyl group; r "" is preferably an alkyl group having 1 to 12 carbon atoms.

[11] The polyaziridine compound according to any of embodiments [1] to [10], wherein the atoms of the connecting chain are C, N, O, S and/or P, preferably C, N and/or O.

[12] The polyaziridine compound according to any of [1] to [11], wherein the number of consecutive C atoms and optionally O atoms between an N atom of a carbamate in structural unit a and another N atom (which is present in the connecting chain or is an N atom of a carbamate of another structural unit a) is at most 9.

[13] The polyethylenimine compound according to any of [1] to [12], wherein the polyethylenimine compound comprises one or more linking groups, wherein each of these linking groups connects two of the structural units a present in the polyethylenimine compound, wherein the linking group consists of at least one functional group selected from the group consisting of:

an aliphatic hydrocarbon functional group (preferably containing from 4 to 10 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing from 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing from 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, an ether functional group, an ester functional group, an amide functional group, a carbonate functional group, a carbamate functional group, a urea functional group, a biuret functional group, an allophanate functional group, a uretdione functional group, and any combination thereof.

[14] The polyaziridine compound according to any of [1] to [13], wherein the linking group consists of at least one functional group selected from the group consisting of: an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, a carbamate functional group, a urea functional group, a biuret functional group, and any combination thereof.

[15] The polyaziridine compound according to any of embodiments [1] to [14], wherein the linking group preferably contains an isocyanurate functional group, an iminooxadiazinedione functional group, or a biuret functional group.

[16] The polyethylenimine compound according to any of [1] to [15], wherein the molecular weight of the polyethylenimine compound is at least 700 daltons, more preferably at least 800 daltons, even more preferably at least 840 daltons, even more preferably at least 1000 daltons, and preferably at most 3800 daltons, more preferably at most 3600 daltons, more preferably at most 3000 daltons, more preferably at most 1600 daltons, even more preferably at most 1200 daltons.

[17] The polyaziridine compound of any of embodiments [1] to [16], wherein the linking group of the polyaziridine compound consists of the following functional groups: at least one aliphatic hydrocarbon function and/or at least one cycloaliphatic hydrocarbon function and optionally at least one aromatic hydrocarbon function and optionally an isocyanurate function or an iminooxadiazinedione function.

[18] The polyaziridine compound of any of [1] to [17], wherein the polyaziridine compound is obtained by reacting compound B having the following structural formula with a polyisocyanate having aliphatic reactivity:

[19] the polyaziridine compound according to embodiment [18], wherein the polyisocyanate with aliphatic reactivity is selected from 1, 5-pentamethylene diisocyanate PDI, 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 4' -dicyclohexylmethane diisocyanate H12MDI, 2, 4-trimethylhexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate TMXDI (all isomers) and higher molecular weight variants such as for example their isocyanurates or iminooxadiazinediones.

[20] The polyaziridine compound of any of [13] to [18], wherein the linking group of the polyaziridine compound consists of an array of consecutive functional groups: an aliphatic hydrocarbon functional group, an aromatic hydrocarbon functional group, and an aliphatic hydrocarbon functional group (e.g., when a polyethylenimine compound is prepared using TMXDI), or the linking group consists of an array of consecutive functional groups: alicyclic hydrocarbon functions, aliphatic hydrocarbon functions and alicyclic hydrocarbon functions (for example when H12MDI is used to make polyazapyridine compounds), or the linking group consists of an array of consecutive functional groups: an aliphatic hydrocarbon functional group, an isocyanurate functional group or an iminooxadiazinedione functional group and an aliphatic hydrocarbon functional group, or the linking group consists of an array of the following successive functional groups: aliphatic hydrocarbon functional groups, isocyanurate functional groups, and aliphatic hydrocarbon functional groups (e.g., when the polyaziridine compound is prepared using the isocyanurate of 1, 6-hexamethylene diisocyanate and/or the isocyanurate of 1, 5-pentamethylene diisocyanate).

[21] The polyaziridine compound according to any of embodiments [1] to [12], wherein the polyaziridine compound according to the present invention is according to the following structural formula:

q is an integer of 2 to 6;

i is a different radical D _i And is an integer from 1 to q;

D _i independently have the following structural formula

Wherein X is NR ₁₁ S or O, wherein R ₁₁ Is H or alkyl having 1 to 4 carbon atoms; y is an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a combination thereof; j is an integer from 1 to p; z is a molecular residue obtained by removing the isocyanate-reactive group XH of the molecule; p is an integer of 0 to 10, m, R', R ₁ 、R ₂ 、R ₃ And R ₄ As defined above, wherein the isocyanate reactive group XH is defined herein as a hydroxyl group (X is O), a primary amine (X is NH), or a secondary amine (X is NR) ₁₁ Wherein R is ₁₁ Alkyl having 1 to 4 carbon atoms) or a thiol (X is S), preferred isocyanate-reactive groups XH are hydroxyl (X is O), primary amine (X is NH) or secondary amine (X is NR) ₁₁ Wherein R is ₁₁ Alkyl groups having 1 to 4 carbon atoms), more preferred isocyanate-reactive groups XH are hydroxyl groups (X is O) and primary amines (X is NH). Preferably, the molecule from which the isocyanate-reactive group is removed to obtain Z is preferably a diol, triol, polyether having terminal isocyanate-reactive groups, polyamide having terminal isocyanate-reactive groups, polycarbonate having terminal isocyanate-reactive groups or polysiloxane having terminal isocyanate-reactive groups, the terminal isocyanate-reactive groups in the polysiloxane having terminal isocyanate-reactive groups being linked to the siloxane by at least one carbon atom, in the case where Z is a molecular residue obtained by removal of an isocyanate-reactive group XH of a diol or triol, said isocyanate-reactive group XH is a hydroxyl group and thus X is O, in the case where Z is a molecular residue obtained by removal of an isocyanate-reactive group XH having a terminal isocyanate-reactive groupIn the case of a molecular residue obtained by removing the isocyanate-reactive groups XH of the polycarbonate having terminal isocyanate-reactive groups, preferably OH and hence X is O, in the case of a molecular residue obtained by reacting the isocyanate-reactive groups XH of the polyether of groups or of the polyamide having terminal isocyanate-reactive groups XH, preferably NH2 (hence X is NH) or OH (hence X is O), and more preferably OH and hence X is O, in the case of Z being a molecular residue obtained by removing the isocyanate-reactive groups XH of the polycarbonate having terminal isocyanate-reactive groups, and in the case of j being greater than 1, then Z may be the same or different, preferably q is 2 or 3, and more preferably q is 1, preferably p is an integer from 0 to 10, more preferably from 0 to 5, even more preferably from 0 to 3, and most preferably p is 0 and m is 0.

[22]A polyaziridine compound having 2 to 6, preferably 2 to 4, more preferably 2 to 3 as in embodiment [1]Structural unit (A) as defined in (1), wherein R ₁ 、R ₂ 、R ₃ 、R ₄ R ', R' and m are as in embodiment [1]]To [10]]Any of the above definitions, wherein the molecular weight of the polyethylenimine compound is from 600 daltons to 5000 daltons, preferably at least 700 daltons, more preferably at least 800 daltons, even more preferably at least 840 daltons and preferably at most 3800 daltons, more preferably at most 3600 daltons, more preferably at most 3000 daltons, more preferably at most 1600 daltons, even more preferably at most 1200 daltons, and wherein the polyethylenimine compound further comprises one or more linking groups, wherein each of these linking groups links two structural units a in structural unit a, wherein said linking group consists of at least one functional group selected from the group consisting of: an aliphatic hydrocarbon function (preferably containing from 1 to 8 carbon atoms), an alicyclic hydrocarbon function (preferably containing from 4 to 10 carbon atoms), an aromatic hydrocarbon function (preferably containing from 6 to 12 carbon atoms), an isocyanurate function, an iminooxadiazinedione function, an ether function, an ester function, an amide function, a carbonate function, a carbamate function, a urea function, a biuret function, an allophanate functionUretdione functional groups, and any combination thereof.

[23] The polyaziridine compound of embodiment [22], wherein the linking group of the polyaziridine compound consists of at least one functional group selected from the group consisting of: an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, a carbamate functional group, a urea functional group, a biuret functional group, and any combination thereof.

[24] The polyaziridine compound according to embodiment [22] or [23], wherein the linking group preferably contains an isocyanurate functional group, an iminooxadiazinedione functional group or a biuret functional group.

[25] The polyaziridine compound of any of [22] to [23], wherein the linking group of the polyaziridine compound consists of the following functional groups: at least one aliphatic hydrocarbon function and/or at least one cycloaliphatic hydrocarbon function and optionally at least one aromatic hydrocarbon function and optionally an isocyanurate function or an iminooxadiazinedione function.

[26] The polyethylenimine compound of any of embodiments [22] to [25], wherein the polyethylenimine compound further comprises one or more linking chains, wherein each of these linking chains connects two of the structural units a present in the polyethylenimine compound, wherein the linking chain preferably consists of 2 to 300 atoms, more preferably consists of 5 to 250 atoms, most preferably consists of 6 to 100 atoms.

[27] The polyaziridine compound according to embodiment [26], wherein the number of consecutive C atoms and optionally O atoms between an N atom of a carbamate in structural unit a and another N atom (which is present in the connecting chain or is an N atom of a carbamate of another structural unit a) is at most 9.

[28] The polyaziridine compound of embodiments [22] to [27], wherein the polyaziridine compound is obtained by reacting compound B having the following structural formula with a polyisocyanate having aliphatic reactivity:

[29] the polyaziridine compound of embodiment [28], wherein the aliphatically reactive polyisocyanate is selected from 1, 5-pentamethylene diisocyanate PDI, 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 4' -dicyclohexylmethane diisocyanate H12MDI, 2, 4-trimethylhexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate TMXDI (all isomers) and higher molecular weight variants such as, for example, their isocyanurates or iminooxadiazinediones.

[30] The polyethylenimine compound of embodiment [28], wherein the linking group of the polyethylenimine compound consists of the following array of consecutive functional groups: an aliphatic hydrocarbon functional group, an aromatic hydrocarbon functional group, and an aliphatic hydrocarbon functional group (e.g., when a polyethylenimine compound is prepared using TMXDI), or the linking group consists of an array of consecutive functional groups: alicyclic hydrocarbon functions, aliphatic hydrocarbon functions and alicyclic hydrocarbon functions (for example when H12MDI is used to make polyazapyridine compounds), or the linking group consists of an array of consecutive functional groups: an aliphatic hydrocarbon functional group, an isocyanurate functional group or an iminooxadiazinedione functional group and an aliphatic hydrocarbon functional group, or the linking group consists of an array of the following successive functional groups: aliphatic hydrocarbon functional groups, isocyanurate functional groups, and aliphatic hydrocarbon functional groups (e.g., when the polyaziridine compound is prepared using the isocyanurate of 1, 6-hexamethylene diisocyanate and/or the isocyanurate of 1, 5-pentamethylene diisocyanate).

[31]A polyaziridine compound having 2 to 6, preferably 2 to 4, more preferably 2 to 3 as in embodiment [1]Structural unit (A) as defined in (1), wherein R ₁ 、R ₂ 、R ₃ 、R ₄ R ', R' and m are as in embodiment [1]]To [10]]Any of the above definitions, wherein the polyaziridine compound has a molecular weight of 600 daltons to 5000 daltons, preferably at least 700 daltons, more preferably at least 800 daltons, even more preferably at least 840 daltons and preferably at most 3800 daltons, more preferably at most 3600 daltons, more preferably at most 3000 daltons, more preferably at most 1600 daltons, even more preferably at most 1200 daltons, and wherein the polyaziridine compound is obtained by reacting at least a polyisocyanate with compound B having the following structural formula:

wherein the molar ratio of compound B to polyisocyanate is from 2 to 6, more preferably from 2 to 4, and most preferably from 2 to 3, and wherein m, R', R ", R ″ ₁ 、R ₂ 、R ₃ And R ₄ As in embodiment [1]]To [10]]As defined in any one of the above.

[32] The polyaziridine compound according to embodiment [31], wherein the polyisocyanate is an aliphatically reactive polyisocyanate, preferably selected from 1, 5-pentamethylene diisocyanate PDI, 1, 6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 4' -dicyclohexylmethane diisocyanate H12MDI, 2, 4-trimethylhexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate TMXDI (all isomers) and higher molecular weight variants such as for example their isocyanurates or iminooxadiazinediones.

[33] The polyaziridine compound of embodiment [31] or [32], wherein compound B is obtained by reacting at least a non-OH functional monoepoxide compound with an aziridine having the following structural formula:

wherein R is ₁ 、R ₂ 、R ₃ And R ₄ As in embodiment [1]Or [2]]To [7]]Preferably the non-OH functional monoepoxide compound is selected from the group consisting of: ethylene oxide, propylene oxide, 2-ethyl ethylene oxide, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl neodecanoate and any mixtures thereof.

[34]According to [1]]To [33]]The polyaziridine compound of any embodiment of (1), wherein the polyaziridine compound contains polyoxypropylene (-O-CHCH 3-CH 2-) _x Radical or polytetrahydrofuran (-O-CH 2-CH 2) _x A radical or preferably polyoxyethylene (-O-CH 2-) _x A group or a polyoxypropylene (-O-CHCH 3-CH 2-) in an amount of at least 0.1% by weight, more preferably at least 6% by weight, more preferably at least 10% by weight and preferably less than 45% by weight, more preferably less than 25% by weight and most preferably less than 16% by weight relative to the polyethylenimine compound _x Radical or polytetrahydrofuran (-O-CH 2-CH 2) _x Radical or preferably polyoxyethylene (-O-CH 2-CH 2-) _x A group.

[35]According to [1]]To [34 ]]The polyaziridine compound of any embodiment of (1), wherein M is in the polyaziridine compound as defined above _n Above 2200 daltons, preferably M _n The amount of alkoxy poly (ethylene glycol) (preferably methoxy poly (ethylene glycol) (MPEG)) and/or poly (ethylene glycol) (PEG) chains above 1600 daltons is preferably less than 35 wt%, more preferably less than 15 wt%, more preferably less than 5 wt%, and most preferably 0 wt%, and the M of the methoxy poly (ethylene glycol) (MPEG) and/or poly (ethylene glycol) (PEG) chains present in the polyaziridine compound is preferably less than 35 wt%, more preferably less than 15 wt%, more preferably less than 5 wt%, and most preferably 0 wt% _n Preferably less than 1100 daltons, more preferably less than 770 daltons, and most preferably less than 570 daltons.

[36] The polyaziridine compound according to any of embodiments [1] to [35], wherein the amount of urethane linkages in the polyaziridine compound is at least 5 wt%, more preferably at least 5.5 wt%, more preferably at least 6 wt%, more preferably at least 9 wt%, more preferably at least 12 wt%, and preferably less than 25 wt%, preferably less than 20 wt%, and preferably the aziridine equivalent weight of the polyaziridine compound (molecular weight of polyaziridine divided by number of aziridine groups) is at least 200 daltons, more preferably at least 230 daltons and even more preferably at least 260 daltons, and preferably at most 2500 daltons, more preferably at most 1000 daltons and even more preferably at most 500 daltons.

[37] A crosslinker composition comprising at least one polyaziridine compound according to any one of embodiments [1] to [36], wherein the molecular weight of the polyaziridine compound according to any one of [1] to [36] present in the crosslinker composition is in the range of 600 daltons to 5000 daltons, preferably at most 3800 daltons, preferably the molecular weight is at most 3800 daltons, more preferably at most 3600 daltons, more preferably at most 3000 daltons, more preferably at most 1600 daltons, even more preferably at most 1200 daltons, and the molecular weight is preferably at least 700 daltons, more preferably at least 800 daltons, even more preferably at least 840 daltons, and most preferably at least 1000 daltons; preferably the average number of aziridinyl groups per molecule of aziridinyl-containing groups in the composition is at least 1.8, preferably at least 2, more preferably at least 2.2, and preferably less than 10, more preferably less than 6 and most preferably less than 4, most preferably the average number of aziridinyl groups per molecule of aziridinyl-containing groups in the composition is from 2.2 to 3.

[38] The crosslinker composition comprising at least one polyaziridine compound according to any of embodiments [1] to [37], wherein the calculated average amount of urethane linkages present in the polyaziridine compound is at least 5 wt. -%, more preferably at least 5.5 wt. -%, more preferably at least 6 wt. -%, more preferably at least 9 wt. -%, more preferably at least 12 wt. -%, and preferably less than 25 wt. -%, preferably less than 20 wt. -%, relative to the total weight of the polyaziridine compound present in the composition.

[39] The crosslinker composition comprising at least one polyaziridine compound according to any of embodiments [1] to [38], wherein the amount of aziridine functional molecules having a molecular weight of less than 250 dalton, more preferably less than 350 dalton, even more preferably less than 450 dalton, even more preferably less than 550 dalton and even more preferably less than 580 dalton with respect to the total weight of the crosslinker composition is less than 5 wt.%, more preferably less than 2 wt.%, more preferably less than 1 wt.%, more preferably less than 0.5 wt.% and most preferably less than 0.1 wt.%, wherein the molecular weight is determined using LC-MS as described in the experimental section below.

[40] A composition comprising a polyaziridine, wherein the polyaziridine has at least two of the following structural units (a):

wherein

R ₁ Is H;

R ₂ and R ₄ Selected from the group consisting of H, aliphatic (alicyclic) groups containing from 1 to 8 carbon atoms and optionally containing one or more heteroatoms in the chain, phenyl, benzyl and pyridyl;

R ₃ is an aliphatic (alicyclic) group containing 1 to 8 carbon atoms and optionally containing one or more heteroatoms in the chain, phenyl, benzyl and pyridyl;

or R ₂ And R ₃ (in R) ₂ In the case where it is different from H) may be part of the same saturated cycloaliphatic group;

r' = H or alkyl having 1 to 12 carbon atoms;

r "= H, aliphatic group having 1 to 12 carbon atoms, alicyclic group having 5 to 12 carbon atoms, aromatic group having 6 to 12 carbon atoms, CH ₂ -O-(C＝O)-R”'、CH ₂ -O-R "" or CH ₂ -(OCR””'HCR””'H) _n -OCH ₃ Wherein R' "and R" "are independently alkyl having 1 to 12 carbon atoms, n is 1 to 35, and R" "is independently H or has 1 to 12 carbon atomsAlkyl groups of the molecule;

or R 'and R' can be part of the same saturated cycloaliphatic radical containing from 5 to 8 carbon atoms;

m is an integer of 1 to 35,

wherein the aziridine groups present in the polyaziridine are linked by at least one chain of atoms which is free of (thio) ester functional groups and free of dithioester functional groups and free of disulfide functional groups, meaning that the aziridine groups linked by the chain of atoms are linked by bonds which are not part of ester, thioester, dithioester and disulfide groups, and are preferably also not part of (thio) amide groups, preferably also not part of acetal groups, and preferably also not part of phosphate (phosphonate) groups; and is

Wherein the number average molecular weight of the composition is in the range of 550 daltons to 5000 daltons.

[41] The composition according to embodiment [40], wherein a pendant group containing a (thio) ester functional group, which is prepared from an acid, is not present on the chain of atoms connecting the aziridine group, in particular, it is preferable that a pendant group containing a (thio) ester functional group, which is prepared from an acid, is not present on the chain of atoms connecting the aziridine group, wherein the carbon atom adjacent to the carbonyl group is a secondary carbon atom.

[42] The composition according to embodiment [40] or [41], wherein the polyaziridines present in the polyaziridine compositions according to the invention are defined molecules, wherein said polyaziridines preferably contain at least 3 said structural units (a) and preferably less than 10 said structural units (a), more preferably less than 6 said structural units (a) and more preferably less than 4 said structural units (a), most preferably said polyaziridines contain 3 said structural units (a).

[43] The composition according to any of embodiments [40] to [42], wherein the polyaziridine composition according to the invention is a mixture of defined molecules and the average amount of structural units (a) present in the polyaziridine is preferably at least 2.2 and preferably less than 10, more preferably less than 6 and most preferably less than 4, preferably the structural units (a) present in the polyaziridine are preferably identical to each other.

[44] The compound according to any of embodiments [40] to [43], wherein the average amount of urethane bonds present in the polyaziridine is at least 5 wt.%, more preferably at least 5.5 wt.%, more preferably at least 6 wt.%, more preferably at least 9 wt.%, more preferably at least 12 wt.%, and preferably less than 25 wt.%, preferably less than 20 wt.% (relative to the total amount of polyaziridine present in the composition), wherein preferably a polyisocyanate having at least 2 isocyanate groups is used to prepare the polyaziridine composition according to the invention, the amount of polyisocyanate having at least 2 isocyanate groups being preferably >50 wt.%, more preferably >80 wt.%, most preferably >100 wt.%, relative to the total amount of isocyanate-containing compounds used to prepare the polyaziridine composition.

[45] The composition according to any of [40] to [44], wherein the aziridine groups present in the polyaziridine are linked by at least one chain of atoms free of (thio) amide functionality, free of acetal functionality and free of phosphate (phosphonate) functionality, and preferably the chain of atoms linking the two aziridine groups Q of the polyaziridine preferably has from 4 to 50 atoms (excluding the atoms of the aziridine group), more preferably from 16 to 34 atoms.

[46]According to [ 40)]To [45]]The composition of any embodiment of (1), wherein R ₄ Is H, and R ₂ And R ₃ Are part of the same saturated cycloaliphatic radical, or R ₂ Is H, R ₃ Is CH ₃ And R is ₄ Is H or CH ₃ More preferably R ₄ Is H.

[47] The composition according to any of [40] to [45], wherein m is an integer from 1 to 35, preferably m is an integer from 1 to 6, more preferably m is an integer from 1 to 4, most preferably m =1.

[48]According to [ 40)]To [47]]The composition of any embodiment of (1), wherein n is an integer from 6 to 20, and preferably R' is H and R "= alkyl having 1 to 8 carbon atoms (preferably CH) ₃ Or CH ₂ CH ₃ )、CH ₂ -O- (C = O) -R' "or CH ₂ -O-R "" or CH ₂ -(OCH ₂ CH ₂ ) _n -OCH ₃ And R' "is an alkyl group having 3 to 12 carbon atoms, more preferably a branched alkyl group having 3 to 12 carbon atoms, and R" "is an alkyl group having 1 to 12 carbon atoms, more preferably R" "is CH ₂ -O-(C＝O)-R”'、CH ₂ -O-R "" or CH ₂ -(OCH ₂ CH ₂ ) _n -OCH ₃ 。

[49] The composition according to any of [40] to [48], wherein the number average molecular weight of the polyethylenimine-containing composition (and/or of the polyethylenimine present in the polyethylenimine composition) is in the range of 550 daltons to 5000 daltons, preferably at most 3000 daltons, more preferably at most 1600 daltons, even more preferably at most 1200 daltons, and preferably at least 840 daltons and most preferably at least 1000 daltons, wherein the number average molecular weight of the polyethylenimine-containing composition is the number average molecular weight of the aziridine functional group molecules and optional byproducts obtained during the preparation of the polyethylenimine present in the polyethylenimine composition and the number average molecular weight is determined using MALDI-TOF mass spectrometry.

[50] The composition according to any of [40] to [49], wherein the amount of aziridine functional molecules having a molecular weight of less than 550 daltons, more preferably less than 700 daltons, even more preferably less than 840 daltons, is preferably less than 5 wt. -%, more preferably less than 2 wt. -%, more preferably less than 1 wt. -%, more preferably less than 0.5 wt. -%, most preferably less than 0.1 wt. -%, relative to the total weight of the polyaziridine-containing composition.

[51] The composition according to any of [40] to [50], wherein the total amount of cyclic structures (other than aziridine groups), which are preferably isocyanurate rings, present in the polyaziridine is preferably 0 to 3, more preferably 0 to 2, even more preferably 1 or 2, most preferably 1.

[52] The composition of any of embodiments [40] to [51], wherein the polyaziridine is obtained by reacting a polyisocyanate with at least one beta-hydroxyalkylene aziridine according to the structure Q-CHR' -CHR "-OH, wherein Q is according to the structural formula

Wherein R ', R', R ₁ 、R ₂ 、R ₃ And R ₄ And embodiment [50]]、[54]Or [56]Is the same as in any of the above.

[53] The composition of any of embodiments [40] to [52], wherein the polyisocyanate contains at least 2 isocyanate groups, preferably an average of 2.5 isocyanate groups, more preferably an average of at least 2.8 isocyanate groups; preferably the polyisocyanate is selected from the group consisting of: isocyanurates of aliphatic diisocyanates that do not contain cyclic groups, iminooxadiazinedione trimers, biuret trimers of aliphatic diisocyanates that do not contain cyclic groups, and any mixtures thereof; more preferably, the polyisocyanate is an isocyanurate or iminooxadiazinedione trimer of a linear (unbranched aliphatic) diisocyanate; even more preferably, the polyisocyanate is selected from the group consisting of: isocyanurates or iminooxadiazinediones of 1, 6-hexamethylene diisocyanate, isocyanurates of 1, 5-pentamethylene diisocyanate, and any mixtures thereof.

[54]According to [52]]To [53]]The composition of any embodiment of (1), wherein the beta-hydroxyalkylene aziridine is prepared by reacting at least one non-OH functional monoepoxide compound with a compound of formula (la)

Wherein R is as defined above, wherein R is as defined above ₁ 、R ₂ 、R ₃ And R ₄ As defined above.

[55] The composition according to any of [40] to [54], wherein the average amount of aziridinyl groups Q present in the polyaziridine composition is at least 1.9, preferably at least 2.5, more preferably at least 2.7, more preferably at least 2.8, more preferably at least 2.9, and preferably less than 6.1, more preferably less than 5, and most preferably less than 3.5.

[56] The composition according to any of [40] to [55], wherein the polyaziridine is obtained by reacting at least the following reactants:

(i) Adducts of aziridines with at least non-OH-functional monoepoxide compounds, and

(ii) A polyisocyanate, preferably in an amount of 20 to 67 wt.% (relative to the total weight of the reactants), wherein the number average molecular weight of the polyethylenimine composition is at most 5000 daltons, preferably at most 3000 daltons, more preferably at most 1600 daltons, more preferably at most 1200 daltons and at least 550 daltons, more preferably at least 840 daltons, most preferably at least 1000 daltons, and the polydispersity is preferably less than 10, more preferably less than 5, even more preferably less than 2, and wherein the polyisocyanate is preferably a triisocyanate, more preferably the polyisocyanate is selected from the group consisting of: isocyanurate of 1, 6-hexamethylene diisocyanate, isocyanurate of 1, 5-pentamethylene diisocyanate, and any mixture thereof; the aziridine is preferably propyleneimine (CAS No. 75-55-8) or 2, 2-dimethylaziridine (CAS No. 2658-24-4), and more preferably the aziridine is propyleneimine.

[57] The composition of embodiment [56], wherein the non-OH functional monoepoxide is selected from the group consisting of: ethylene oxide, propylene oxide, 2-ethylethylene oxide, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl neodecanoate and any mixtures thereof.

[58] The composition according to any of the embodiments [40] to [57], wherein the polyethylenimine present in the composition contains oxyethylene (-O-CH 2-) groups and/or oxypropylene (-O-CHCH 3-CH 2-) groups, preferably in an amount of at least 0.1 wt. -%, more preferably of at least 6 wt. -%, more preferably of at least 10 wt. -%, and in an amount of preferably less than 45 wt. -%, more preferably of less than 25 wt. -% and most preferably of less than 16 wt. -% (relative to the total amount of polyethylenimine present in the composition), preferably the polyethylenimine present in the composition contains oxyethylene (-O-CH 2-) groups, preferably in an amount of at least 0.1 wt. -%, more preferably of at least 6 wt. -%, more preferably of at least 10 wt. -%, and in an amount of preferably of less than 75 wt. -%, more preferably of less than 35 wt. -% and most preferably of less than 20 wt.% (relative to the total amount of polyethylenimine present in the composition).

[59]According to [ 40)]To [58]]The composition of any embodiment of (1), wherein M is in the polyaziridine _n Above 2200 daltons, preferably M _n The amount of alkoxy poly (ethylene glycol) (preferably methoxy poly (ethylene glycol) (MPEG)) and/or poly (ethylene glycol) (PEG) chains above 1600 daltons is preferably less than 35 wt%, more preferably less than 15 wt%, more preferably less than 5 wt%, and most preferably 0 wt%, and preferably the M of the methoxy poly (ethylene glycol) (MPEG) and/or poly (ethylene glycol) (PEG) chains present in the cross-linking agent _n Preferably less than 1100 daltons and more preferably less than 570 daltons.

[60] The composition of any of embodiments [40] to [59], wherein the composition comprises less than 15 wt.%, preferably less than 5 wt.%, more preferably less than 1 wt.%, and most preferably less than 0.1 wt.% water.

[61] The composition according to any of embodiments [40] to [60], wherein the polyethylenimine in its 100% form (without any diluents such as solvents and plasticizers) preferably has a brookfield viscosity at 25 ℃ of at least 500mpa.s, more preferably at least 1200mpa.s, more preferably at least 3000mpa.s, and at 25 ℃ of preferably at most 1000000mpa.s, more preferably at most 100000mpa.s, more preferably at most 30000mpa.s, more preferably at most 10001000mPa.s and most preferably at least 5000mpa.s, wherein the brookfield viscosity is determined according to ISO 2555-89. In an alternative embodiment, the viscosity of the polyaziridine is measured with a Brookfield with spindle S63 at 25 ℃ in 80% solids, 20% Dimethylformamide (DMF); the viscosity measured according to this method is preferably in the range of 300mpa.s to 20000mpa.s, more preferably in the range of 500mpa.s to 12000mpa.s, and most preferably in the range of 700mpa.s to 3000 mpa.s.

[62] The composition of any of [40] to [61], wherein the polyethylenimine present in the composition is a crosslinking agent suitable for crosslinking a carboxylic acid functional polymer.

[63] Use of a composition as defined in any of embodiments [1] to [62] for crosslinking a carboxylic acid functional polymer dissolved and/or dispersed in an aqueous medium.

[64] A multi-pack system comprising a first pack comprising a carboxylic acid functional polymer dissolved and/or dispersed in an aqueous medium and a second pack comprising a composition as defined in any of embodiments [1] to [66], wherein the first pack and the second pack are stored separately.

[68] A coating composition obtained by mixing a first pack and a second pack of a multi-pack system according to embodiment [64] just prior to application of the coating composition, wherein the coating composition comprises aziridinyl groups Q and carboxylic acid groups in amounts such that the Stoichiometric Amount (SA) of aziridinyl groups Q on carboxylic acid groups is from 0.1 to 2.0, more preferably from 0.2 to 1.5, even more preferably from 0.25 to 0.95, most preferably from 0.3 to 0.8.

[69] A substrate having a coating, said coating being obtained by: (i) Applying the coating composition according to embodiment [68] to a substrate, and (ii) drying the coating composition by evaporating volatiles.

The invention will now be illustrated by reference to the following examples. All parts, percentages and ratios are on a weight basis unless otherwise indicated.

Components and abbreviations used:

N3600、

N3900、

n3400 and

XP2860 was obtained from Covestro.

(. + -.) -allyl-2, 3-epoxypropyl ether (allyl glycidyl ether, CAS number 106-92-3) was obtained from Acros Organics (a subsidiary of the mo Fisher Scientific).

N-butyl glycidyl ether (CAS No. 2426-08-6) was obtained from Alfa Aesar (a subsidiary of the mo Fisher Scientific).

Dimethylformamide (68-12-2) was obtained from Acros Organics (a subsidiary of the mo Fisher Scientific).

Di (propylene glycol) dimethyl ether (Proglyde DMM, CAS number 111109-77-4) was obtained from Dow Inc.

O-toluene glycidyl ether (CAS number 2210-79-9) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

Both mPEG-epoxide with MW of 550Da (methoxy PEG-epoxide) and mPEG-epoxide with MW of 1kDa were obtained from Creative PEGWorks (Chapel Hill, north Carolina, USA).

Trans 2, 3-epoxybutane (CAS number 21490-63-1) was obtained from abcr GmbH (Karlsruhe, germany).

2-Ethyl oxirane (1, 2-epoxybutane, CAS number 106-88-7) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

Cyclohexene oxide (CAS number 286-20-4) was obtained from Sigma-Aldrich (subsidiary of Merck KGaA).

Polyethylene glycol monomethyl ether having a number average molecular weight of 350Da (CAS number 9004-74-4) was obtained from Alfa Aesar (a subsidiary of the mo Fisher Scientific), polyethylene glycol monomethyl ether having a number average molecular weight of 500Da was obtained from Acros Organics (a subsidiary of the mo Fisher Scientific), polyethylene glycol monomethyl ether having a number average molecular weight of 750Da was obtained from Acros Organics (a subsidiary of the mo Fisher Scientific), polyethylene glycol monomethyl ether having a number average molecular weight of 1000Da was obtained from Tokyo Chemical Industry Co., ltd., and polyethylene glycol monomethyl ether having a number average molecular weight of 2000Da was obtained from Tokyo Chemical Industry Co., ltd.

2-ethylhexyl glycidyl ether (CAS number 2461-15-6) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

2-Methyltetrahydrofuran (CAS number 96-47-9) was obtained from Merck KgaA.

Potassium carbonate (CAS number 584-08-7) was obtained from Alfa Aesar (a subsidiary of the same Fisher Scientific).

Cardura E10P (CAS No. 26761-45-5) was obtained from Hexion Inc.

Polypropylene glycol-based aqueous polyurethane dispersions with an acid number of 6.26mg KOH/g

R-1005 is obtained from DSM.

Agisyn 2844 (ethoxylated (5) pentaerythritol tetraacrylate, CAS number 51728-26-8) was obtained from DSM.

DBTDL (dibutyltin dilaurate, CAS No. 77-58-7) was obtained from Reaxis.

H12MDI (4, 4' -methylene bis (phenyl isocyanate,

w, CAS number 101-66-8) from Covestro.

Trimethylolpropane tris (2-methyl-1-aziridinepropionate), CAS No. 64265-57-2, CX-100, obtained from DSM.

2, 2-Dimethylaziridine (CAS number 2658-24-4) was obtained from amine LLC (Monmouth Jct., NJ, united States of America).

2-Methylaziridine (propyleneimine, CAS No. 75-55-8) was obtained from Menadiona S.L. (Palafols, spain).

1, 3-bis (2-isocyanatopropan-2-yl) benzene (m-tetramethylxylene diisocyanate, TMXDI, CAS number 2778-42-9) was obtained from Allnex.

HDI (1, 6-Hexane diisocyanate, CAS No. 822-06-0) was obtained from Acros Organics (a subsidiary of the mo Fisher Scientific).

IPDI (5-isocyanato-1- (isocyanatomethyl) -1, 3-trimethylcyclohexane,

i, isophorone diisocyanate, CAS No. 4098-71-9) was obtained from Covestro.

TMP (1, 1-tris (hydroxymethyl) propane, CAS number 77-99-6) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

TDI (toluene diisocyanate, CAS number 26471-62-5,

an 80/20 mixture of T80,2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate) was obtained from Covestro.

Durez-ter S105-110 (polyester polyol having an OH number of 110mg KOH/g based on adipic acid and hexanediol) was obtained from Sumitomo Bakelite.

pTHF650 (polytetramethylene ether glycol having an OH number of 172mg KOH/g) was obtained from BASF.

Bismuth neodecanoate (CAS number 34364-26-6) was obtained from TIB chemicals AG (Mannheim, germany).

Phenothiazine (CAS No. 92-84-2) was obtained from Sigma-Aldrich (subsidiary of Merck KGaA).

1-Butanol (CAS number 71-36-3) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

1-methyl-2-propanol acetate (propylene glycol methyl ether acetate, CAS number 108-65-6) was obtained from Shell Chemicals.

Hydrazine (16% aqueous solution, CAS number 302-01-2) was obtained from Honeywell.

Dimethylolpropionic acid (DMPA, CAS No. 4767-03-7) was obtained from Perstop polymers.

Triethylamine (TEA, CAS number 121-44-8) was obtained from Arkema.

Sodium lauryl sulfate (30% aqueous, CAS number 73296-89-6) was obtained from BASF.

Methyl methacrylate (CAS number 80-62-6) was obtained from Lucite Int.

N-butyl acrylate (CAS number 141-32-2) was obtained from Dow Chemical.

Methacrylic acid (CAS number 79-41-4) was obtained from Lucite Int.

Ammonium persulfate (CAS number 7727-54-0) was obtained from United Initiators.

Ammonia (25% in water, CAS No. 1336-21-6) was obtained from Merck.

Dipropylene glycol dimethyl ether (CAS number 34590-94-8) was obtained from Dow Chemical.

2-methyl-1, 3-propanediol (CAS number 2163-42-0) was obtained from Lyondell.

1, 4-butanediol (CAS number 110-63-4) was obtained from BASF.

Adipic acid (CAS No. 124-04-9) was obtained from BASF.

LC-MS

LC-MS analysis of the low molecular weight fraction was performed using the following procedure:

a methanol solution of about 100mg/kg of material was gravimetrically prepared and stirred. Mu.l of this solution was injected into UPLC equipped with ESI-TOF-MS detection. The column used was 100X 2.1mm,1.8um, waters HSS T3C 18 operating at 40 ℃. The flow rate was 0.5ml.min-1. The solvent used was 10mM NH ₄ CH ₃ COO (with NH) ₃ Set to pH 9.0, elute A), acetonitrile (B) and THF (C). 2 binary gradients from 80/20A/B to 1/99A/B in 10 min and from 1/99A/B to 1/49/50A/B/C in 5 min were applied, after which the starting conditions (80/20A/B) were applied. The total ion current signal was integrated assuming that all components had a linear MS response over all response ranges and that all components were equally ionized in efficiency. In the case of co-elution, the extracted ion chromatogram for that particular species is integrated.

MALDI-ToF-MS

All MALDI-ToF-MS spectra were acquired using a Bruker UltraFlextreme MALDI-ToF mass spectrometer. The instrument was equipped with a Nd: YAG laser emitting at 1064nm and a collision cell (not used for these samples). Spectra were acquired in positive ion mode using a reflectron, using the highest resolution mode (range 60-7000 m/z) that provided accurate mass. Cesium triiodide (range 0.3-3.5 kDa) was used for mass calibration (calibration method: IAV molecular characterization, code MC-MS-05). The laser energy was 20%. The sample was dissolved in THF at about 50 mg/mL. The substrates used were: DCTB (trans 2- [3- (4-tert-butylphenyl) -2-methyl-2-propenylidene ] malononitrile), CAS No. 300364-84-5. The matrix solution was prepared by dissolving 20mg in 1mL THF. Sodium iodide was used as a salt (NaI, CAS No. 7681-82-5) in addition to comparative examples 4, 6 and 8, in which potassium trifluoroacetate (KTFA, CAS No. 2923-16-2) was used as a salt; 10mg are dissolved in 1ml THF and MeOH is added dropwise. Sample: matrix: salt ratio =10 (μ Ι), after mixing, 0.5 μ Ι are spotted onto MALDI plates and air dried. The reported signal is the main peak within 0.5Da of the calculated mass of the polyaziridine compound theoretically present in the maximum amount in the composition. In all cases, the peaks reported are sodium or potassium adducts of the measured ions.

Genotoxicity testing

By passing

The genotoxicity of the examples and comparative examples was evaluated by assay (Toxys, leiden, the Netherlands). The ToxTracker assay is a panel of several validated Green Fluorescent Protein (GFP) -based mouse embryonic stem (mES) reporter cell lines that can be used to identify the biological activity and potentially oncogenic properties of newly developed compounds in a single test. The method uses a two-step process.

In the first step, line dose range finding was performed using wild-type mES cells (line B4418). Each compound was tested at 20 different concentrations, starting with 10mM in DMSO as the highest concentration, and 19 serial 2-fold dilutions.

Next, the genotoxicity of the examples and comparative examples was evaluated using a specific gene linked to a reporter gene for detecting DNA damage; the specific genes are Bscl2 (as elucidated by US9695481B2 and EP2616484B 1) and Rtkn (Hendriks et al, toxicol. Sci.2015,150, 190-203) biomarkers. Genotoxicity was assessed at 10%, 25% and 50% cytotoxicity in the absence and presence of a metabolic system based on rat S9 liver extracts (aroclone 1254 induced rat, moltox, boone, NC, USA). Independent cell lines were seeded into 96-well cell culture plates and fresh ES cell culture medium containing diluted test substance was added to the cells 24 hours after seeding of the cells into 96-well plates. Five concentrations were tested at 2-fold dilutions for each compound tested. The highest sample concentration will induce significant cytotoxicity (50-70%). In the case of no or low cytotoxicity, 10mM or the maximum soluble mixture concentration was used as the maximum test concentration. Cytotoxicity was determined by cell counting using a Guava easyCyte 10HT flow cytometer (Millipore) after 24 hours of exposure.

GFP reporter induction was always compared to vehicle control treatment. For a particular compound, DMSO concentrations in all wells were similar and never exceeded 1%. All compounds were tested in at least three completely independent replicates. A positive control treatment with cisplatin (DNA damage) was included in all experiments. The metabolic performance was assessed by addition of S9 liver extract. Cells were exposed to five concentrations of test compound for 3 hours in the presence of S9 and the required cofactor (regenssa + B, moltox, boone, NC, USA). After washing, the cells were incubated in fresh ES cell culture medium for 24 hours. After 24 hours of exposure, induction of the GFP reporter gene was determined using a Guava easyCyte 10HT flow cytometer (Millipore). GFP expression was only determined in intact single cells. The average GFP fluorescence and cell concentration in each well were measured and used for cytotoxicity assessment. Data were analyzed using toxpalt software (Toxys, leiden, the Netherlands). The levels of induction reported were at concentrations of compounds that induced 10%, 25% and 50% cytotoxicity after 3 hours of exposure and 24 hours recovery in the presence of S9 rat liver extract or alternatively after 24 hours of exposure in the absence of S9 rat liver extract.

A positive induction level of the biomarker is defined as equal to or higher than 2-fold induction at least one of 10%, 25% and 50% cytotoxicity in the absence or presence of metabolic system rat S9 liver extract; a weak positive induction is defined as a more than 1.5-fold and less than 2-fold induction at least one of 10%, 25% and 50% cytotoxicity (but less than 2-fold at 10%, 25% and 50% cytotoxicity) in the absence or presence of metabolic system rat S9 liver extract, and a negative induction is defined as a less than or equal to 1.5-fold induction at 10%, 25% and 50% cytotoxicity in the absence or presence of metabolic system based on rat S9 liver extract.

Comparative example 1

Comparative example 1 is CX-100, trimethylolpropane tris (2-methyl-1-aziridinepropionate).

The chemical structure is shown below.

For reference, the performance of trimethylolpropane tris (2-methyl-1-aziridinepropionate) as a crosslinker was assessed using the spot test on the coating surface, based on procedures from DIN 68861-1 standard. For these tests, 0.23 part of compound is mixed with 0.60 part of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.56 part of the resulting solution was added to 20 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test C1-1). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton (cotton wool) was immersed in 1EtOH: demineralized water and placed on the membrane for various time intervals. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Comparative example 2

508.7 grams of Agisyn 2844 and 0.26 grams of phenothiazine were charged to a stainless steel reactor equipped with a thermostat. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture was then heated to 35 ℃ and 25.3 g of propyleneimine were subsequently added within 30 minutes. The mixture was then further heated to 45 ℃ and held at this temperature for 36 hours. The resulting mixture, with a calculated molecular weight of the main component of 800.48Da, was discharged and tested for genotoxicity. The chemical structure is shown below.

Genotoxicity testing

Comparative example 3

10.0 g of 1, 3-bis (1-isocyanato-1-methylethyl) benzene, 0.02 g of bismuth neodecanoate, 3.56 g of 1- (2-hydroxyethyl) ethylidene imine, 1.83 g of trimethylolpropane and 87 g of dimethylformamide were charged into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture was then heated to 50 ℃, held at that temperature for 15 minutes, and then further heated to 75 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a pale yellow wax. The calculated molecular weights of the theoretical main components are 1127.66Da (three aziridines) and 418.26Da(two aziridines), the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1150.66Da; observed [ M + Na + ] =1150.56Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =441.26Da; observed [ M + Na + ] =441.20Da.

Genotoxicity testing

Comparative example 4

15.0 grams Desmodur N3600 and 75 grams dimethylformamide were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture was then heated to 50 ℃ after which 6.80 g of 1- (2-hydroxyethyl) ethyleneimine were added. After 15 minutes, 0.03g of bismuth neodecanoate was charged into the reaction flask, which was then heated further to 60 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear yellowish high viscosity liquid. The calculated molecular weight of the theoretical main component is 765.47Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + K + ] =804.43Da; observed [ M + K + ] =804.27Da.

Genotoxicity test

Comparative example 5

2.60 g of 1- (aziridin-1-yl) propan-2-ol, 0.02 g of bismuth neodecanoate and 32 g of dimethylformamide were charged into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 5.00 grams Desmodur N3600 in 32 grams dimethylformamide was then added dropwise over 15 minutes to the reaction flask, after which the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain an opaque high viscosity liquid. The calculated molecular weight of the theoretical main component is 807.52Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =830.52Da; observed [ M + Na + ] =830.47Da.

Genotoxicity test

Comparative example 6

9.00 g of 1, 6-hexane diisocyanate and 74 g of 2-methyltetrahydrofuran were charged into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture is then heated to 40 ℃ and, when this temperature is reached, 12.20 g of 1- (2-methylaziridin-1-yl) propan-2-ol are gradually charged. After the sharp exotherm, the reaction temperature was stabilized at 60 ℃ and maintained at that temperature. At regular intervalsSamples were taken and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain an opaque viscous liquid. The theoretical main component has a calculated molecular weight of 398.29Da and a chemical structure shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + K + ] =437.25Da; observed [ M + K + ] =437.20Da.

Genotoxicity testing

Comparative example 7

3.00 g IPDI, 28 g DMF and 3.08 g 1- (2-methylaziridin-1-yl) propan-2-ol were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture was then heated to 50 ℃ and, when this temperature was reached, 0.02 g of bismuth neodecanoate was added. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear high viscosity liquid. The calculated molecular weight of the theoretical main component is 452.34Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =475.34Da; observed [ M + Na + ] =475.32Da.

Genotoxicity test

Comparative example 8

8.95 g of 1- (2-methylaziridin-1-yl) propan-2-ol, 0.02 g of bismuth neodecanoate and 54 g of dimethylformamide were charged into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 10.0 g of 1, 3-bis (1-isocyanato-1-methylethyl) benzene in 54 g of dimethylformamide is then added dropwise over 45 minutes to the reaction flask, after which the mixture is further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear viscous liquid. The calculated molecular weight of the theoretical main component is 474.32Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + K + ] =513.28Da; observed [ M + K + ] =513.19Da.

Genotoxicity testing

Comparative example 9

3.00 g of H12MDI, 27 g of DMF and 2.61 g of 1- (2-methylaziridin-1-yl) propan-2-ol were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture was then heated to 50 ℃ and when this temperature was reached, 0.02 g of bismuth neodecanoate was added. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear high viscosity liquid. The calculated molecular weight of the theoretical main component is 492.37Da, and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =515.37Da; observed [ M + Na + ] =515.35Da.

Genotoxicity test

Example 1

20.0 grams of Desmodur N3600, 11.98 grams of 1- (2-methylaziridin-1-yl) propan-2-ol, and 106 grams of 2-methyltetrahydrofuran were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture was then heated to 50 ℃, held at that temperature for 15 minutes, and then further heated to 60 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear high viscosity liquid. The calculated molecular weight of the theoretical main component is 849.57Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =872.57Da; observed [ M + Na + ] =872.53Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present at 0.06 wt% in the composition.

Genotoxicity testing

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.41 parts of the composition was mixed with 0.60 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.67 part of the resulting solution was added to 20 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 1-1). For reference, films were also cast from the same composition lacking the crosslinker (tests 1-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

The spot test on the surface of coatings with different binder systems was used to assess the performance of the synthesized compounds as crosslinkers.

The aqueous polyurethane adhesive was synthesized as follows.

A1L flask equipped with a thermometer and overhead stirrer was charged with DMPA (13.4 grams), pTHF650 (166.1 grams), and IPDI (156.5 grams). Placing the reaction mixture in N ₂ Heated to 50 ℃ under an atmosphere and 0.03g of bismuth neodecanoate was added. The mixture was allowed to exotherm and held at 90 ℃ for 2.5 hours. The NCO content of the resulting urethane prepolymer was 8.00% by solid (theoretical 8)80%). The prepolymer was cooled to 75 ℃ and TEA (9.12 g) was added and the resulting mixture was stirred for 15 minutes. A dispersion of the resulting prepolymer was prepared by feeding 320.2 grams of the prepolymer to demineralized water (700 grams) at room temperature over 30 minutes. After the feed was complete, the mixture was stirred for 5 minutes and hydrazine (16% aqueous solution, 61.6 g) was added. The dispersion was stirred for an additional 1 hour.

For further spot testing, 0.35 parts of the crosslinker composition was mixed with 0.07 parts of dipropylene glycol methyl ether and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resultant solution was added to 15 parts of the above aqueous polyurethane binder under continuous stirring, and the resultant mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (tests 1-3). For reference, films were also cast from the same compositions lacking the crosslinker (tests 1-4). The film was dried at 25 ℃ for 1 hour, then annealed at 50 ℃ for 16 hours, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

The aqueous acrylic adhesive was synthesized as follows.

A 2L four-necked flask equipped with a thermometer and overhead stirrer was charged with sodium lauryl sulfate (30% solids in aqueous solution, 18.6 grams of solution) and demineralized water (711 grams). The reactor phase was placed in N ₂ Under atmosphere and heated to 82 ℃. A mixture of demineralized water (112 g), sodium lauryl sulfate (30% solids in water, 37.2 g solution), methyl methacrylate (174.41 g), n-butyl acrylate (488.44 g), and methacrylic acid (34.88 g) was placed in a large feed funnel and emulsified with an overhead stirrer (monomer feed).Ammonium persulfate (1.75 g) was dissolved in demineralized water (89.61 g) and placed into a small feed funnel (initiator feed). Ammonium persulfate (1.75 g) was dissolved in demineralized water (10.5 g) and the solution was added to the reactor phase. Immediately thereafter, a 5% by volume feed of monomer was added to the reactor phase. The reaction mixture was then allowed to exotherm to 85 ℃ and held at 85 ℃ for 5 minutes. The residual monomer feed and initiator feed were then fed to the reaction mixture over 90 minutes, maintained at a temperature of 85 ℃. After the feed was complete, the monomer feed funnel was rinsed with demineralized water (18.9 grams) and the reaction temperature was maintained at 85 ℃ for 45 minutes. Subsequently, the mixture was cooled to room temperature and adjusted to pH =7.2 with ammonia solution (6.25 wt% in demineralised water) and to 40% solids with additional demineralised water.

For further spotting, 0.89 parts of the crosslinker composition was mixed with 0.18 parts of dipropylene glycol methyl ether and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 15 parts of the above aqueous polyacrylate binder under continuous stirring, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (tests 1-5). For reference, films were also cast from the same compositions lacking the crosslinker (tests 1-6). The film was dried at 25 ℃ for 1 hour, then annealed at 50 ℃ for 16 hours, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

The polyester binder was synthesized as follows.

A2L reactor equipped with a distillation apparatus, thermometer and overhead stirrer was charged with 2-methyl-1, 3-propanediol (151.9 g), 1, 4-butanediol (152.1 g), adipic acid (446.3 g) and dimerized fatty acid (371.2 g). The reaction mixture was heated to 220 ℃ and the water of reaction was removed by distillation. The remaining water was removed under reduced pressure until the acid number of the mixture was less than 40mg KOH/g. For further mottling tests, 42 parts of polyester binder were mixed with 8.4 parts of methyl ethyl ketone (polyester blend).

For further spotting, 1.93 parts of the crosslinker composition was mixed with 0.39 parts of dipropylene glycol methyl ether and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resultant solution was added to 25.4 parts of the above polyester mixture under continuous stirring, and the resultant mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (tests 1-7). For reference, films were also cast from the same compositions lacking the crosslinker (tests 1-8).

Ethanol spot test

Example 2

5.93 g of 1- (2-methylaziridin-1-yl) propan-2-ol, 0.02 g of bismuth neodecanoate and 40.18 g of 2-methyltetrahydrofuran were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 10.0 g Desmodur N3900 in 40.18 g 2-methyltetrahydrofuran was then added dropwise over 45 minutes to the reaction flask, after which the mixture was heated further to 75 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a pale yellow high viscosity liquid. The calculated molecular weight of the theoretical main component is 849.57Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =872.57Da; observed [ M + Na + ] =872.62Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present at 1.4 wt% in the composition.

Genotoxicity testing

Example 3

2.14 g of 1- (2-methylaziridin-1-yl) propan-2-ol, 2.72 g of poly (ethylene glycol) monomethyl ether with an average Mn of 350Da, 0.02 g of bismuth neodecanoate and 28 g of 2-methyltetrahydrofuran were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 5.13 grams Desmodur N3600 in 28 grams 2-methyltetrahydrofuran was then added dropwise over 45 minutes to the reaction flask, after which the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear high viscosity liquid. The calculated molecular weights of the theoretical main components are 849.57Da (three aziridines), 1074.68Da (two aziridines, 7EG repeat units), 1118.70Da (two aziridines, 8EG repeat units) and 1162.73Da (two aziridines, 9EG repeat units), with the chemical structures shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =872.57Da; observed [ M + Na + ] =872.53Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1097.68Da; observed [ M + Na + ] =1097.63Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1141.70Da; observed [ M + Na + ] =1141.66Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1185.73Da; observed [ M + Na + ] =1185.68Da.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.71 parts of the composition was mixed with 0.60 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.87 part of the resulting solution was added to 20 parts under continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 3-1). For reference, films were also cast from the same composition lacking the crosslinker (test 3-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane,10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 4

A reaction flask equipped with a thermometer was charged with 15.0 grams Desmodur N3600, 7.09 grams 1- (2-methylaziridin-1-yl) propan-2-ol, 8.21 grams poly (ethylene glycol) monomethyl ether having an average Mn of 500Da, and 110 grams 2-methyltetrahydrofuran. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture was then heated to 50 ℃, held at that temperature for 15 minutes, and then further heated to 60 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear high viscosity liquid. The calculated molecular weights of the theoretical main components are 849.57Da (three aziridines), 1250.78Da (two aziridines, 11EG repeat unit), 1294.81Da (two aziridines, 12EG repeat unit) and 1338.84Da (two aziridines, 13EG repeat unit), with the chemical structures shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =872.57Da; observed [ M + Na + ] =872.54Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1273.78Da; observed [ M + Na + ] =1273.76Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1317.81Da; observed [ M + Na + ] =1317.78Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1361.84Da; observed [ M + Na + ] =1361.81Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present in the composition at 0.26 wt%.

Genotoxicity test

The properties of the synthesized compounds as crosslinkers were assessed using the spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.66 parts of the composition was combined with 0.60 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.84 part of the resulting solution was added to 21 parts under continuous stirring

R-1005 and the resulting mixture is further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 4-1). For reference, films were also cast from the same composition lacking the crosslinker (test 4-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

The performance of the synthesized compounds as crosslinkers was assessed using a spot test on the surface of coatings with different binder systems.

For further spot testing, 0.55 parts of the crosslinker composition was mixed with 0.11 parts of dipropylene glycol methyl ether and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 15 parts of the aqueous polyurethane adhesive prepared as described in example 1 under continuous stirring, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 4-3). For reference, films were also cast from the same compositions lacking the crosslinker (tests 4-4). The film was dried at 25 ℃ for 1 hour, then annealed at 50 ℃ for 16 hours, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

For further spot testing, 1.41 parts of the crosslinker composition was mixed with 0.28 parts of dipropylene glycol methyl ether and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 15 parts of the aqueous polyacrylate binder prepared as described in example 1 under continuous stirring, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (tests 4-5). For reference, films were also cast from the same compositions lacking the crosslinker (tests 4-6). The film was dried at 25 ℃ for 1 hour, then annealed at 50 ℃ for 16 hours, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

In another test, 3.07 parts of the crosslinker composition were mixed with 0.61 parts of dipropylene glycol methyl ether and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 25.4 parts of the polyester mixture prepared as described in example 1 above with continuous stirring, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (tests 4-7). For reference, films were also cast from the same compositions lacking the crosslinker (tests 4-8).

All films were dried at 25 ℃ for 1 hour, then annealed at 50 ℃ for 16 hours, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Example 5

A reaction flask equipped with a thermometer was charged with 15.0 grams Desmodur N3600, 7.09 grams 1- (2-methylaziridin-1-yl) propan-2-ol, 8.21 grams poly (ethylene glycol) monomethyl ether having an average Mn of 1000Da, and 112 grams dimethylformamide. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture was then heated to 50 ℃, 0.03g of dibutyltin dilaurate was added, and after 15 minutes the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain an opaque high viscosity liquid. The calculated molecular weights of the theoretical main components are 849.57Da (three aziridines) and 1735.07Da (two aziridines, 22EG repeat units), with chemical structures as shown below.

Genotoxicity testing

Example 6

6.00 grams Desmodur N3600 and 89 grams 2-methyltetrahydrofuran were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere. The mixture was then heated to 50 ℃ and, upon reaching this temperature, 2.84 grams of 1- (2-methylaziridin-1-yl) propan-2-ol, 13.14 grams of poly (ethylene glycol) monomethyl ether with an average Mn of 2000Da and 0.02 grams of bismuth neodecanoate were charged to a reaction flask, which was then further heated to 60 ℃. Sampling at regular intervalsAnd the progress of the reaction was monitored by Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a white solid wax. The calculated molecular weights of the theoretical main components are 849.57Da (three aziridines) and 2747.67Da (two aziridines, 45EG repeat units) and the chemical structures are shown below.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 1.22 parts of the composition was combined with 0.60 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 1.21 parts of the resulting solution was added to 21 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 6-1). For reference, films were also cast from the same composition lacking the crosslinker (test 6-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 7

Place 10mL reaction vial in N ₂ Propyleneimine (2.28 g), 1, 2-epoxybutane (3.40 g) were charged under an atmosphere, capped, and heated to 55 ℃, after which the mixture was stirred at T =55 ℃ for 4 days. Excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

A reaction flask equipped with a thermometer was charged with 1.62 grams Desmodur N3600, 0.02 grams bismuth neodecanoate, and 8.20 grams dimethylformamide. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 1.04 grams of the product from the first step in 8.20 grams of dimethylformamide was then added dropwise over 15 minutes to the reaction flask, and 8.20 grams of dimethylformamide was flushed into the reaction mixture through the addition funnel, and the mixture was further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No change in NCO elongation was observed. Subsequently, 0.05 g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above NCO stretching peak. The solvent was evaporated in vacuo to 30% solids to give a clear liquid. The theoretical main component has a calculated molecular weight of 891.62Da and a chemical structure shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =914.62Da; observed [ M + Na + ] =914.66Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present at 0.09 wt% in the composition.

Based on a signal from DIN68861-1 Standard procedure the spot test on the coated surface was used to assess the performance of the synthesized compounds as cross-linkers. For these tests, 1.56 parts of the composition (i.e., at 30% solids in dimethylformamide) was added to 15 parts with continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 7-1). For reference, films were also cast from the same composition lacking the crosslinker (test 7-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Example 8

A20 mL reaction vial was charged with propyleneimine (2.95 g), trans 2, 3-epoxybutane (3.75 g) and K ₂ CO ₃ (1.0 g), capped, heated to 55 ℃, and the mixture was stirred at T =55 ℃ for 11 days. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

0.96 grams Desmodur N3600, 0.02 grams bismuth neodecanoate, and 4.90 grams dimethylformamide were charged to a reaction flask equipped with a thermometer. Mechanically treating the mixture under nitrogen atmosphereThe stirrer was stirred and heated to 50 ℃. A solution of 0.62 grams of the product from the first step in 4.90 grams of dimethylformamide was then added dropwise over 15 minutes to the reaction flask, and 4.90 grams of dimethylformamide was flushed into the reaction mixture through the feed funnel, and the mixture was then further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 Until no change in NCO elongation was observed. Subsequently, 0.03g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above-mentioned NCO stretching peak. The solvent was evaporated in vacuo to 45% solids to give a low viscosity pink liquid. The theoretical main component has a calculated molecular weight of 891.62Da and a chemical structure shown below.

The properties of the synthesized compounds as crosslinkers were assessed using the spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 1.01 parts of the composition (i.e. at 45% solids in dimethylformamide) was added to 15 parts with continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 8-1). For reference, films were also cast from the same composition lacking the crosslinker (test 8-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Example 9

A reaction vial was charged with propyleneimine (3.53 g), allyl glycidyl ether (5.07 g) and K ₂ CO ₃ (0.5 g), capped and heated to 80 ℃, then the mixture was stirred at T =80 ℃ for 20 hours. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

4.0 grams of Desmodur N3600, 0.02 grams of bismuth neodecanoate and 7.50 grams of dimethylformamide were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 3.41 grams of the product from the first step in 7.50 grams of dimethylformamide was then added dropwise over 10 minutes to the reaction flask, and 7.50 grams of dimethylformamide was flushed into the reaction mixture through the feed funnel, and the mixture was then further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 Until no change in NCO elongation was observed. Subsequently, 0.13 g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above NCO stretching peak. The resulting solution was a clear liquid. The calculated molecular weight of the theoretical main component is 1017.65Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1040.64Da; observed [ M + Na + ] =1040.75Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.098% by weight, and

present in the composition at less than 0.01 wt%.

Genotoxicity testing

Example 10

A1L round bottom flask equipped with a condenser was placed in N ₂ Under atmosphere, and charged with propyleneimine (80.0 g), n-butyl glycidyl ether (126.0 g) and K ₂ CO ₃ (10.00 g) and heated to 80 ℃ over 30 minutes, after which the mixture was stirred at T =80 ℃ for 21 hours. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

46.54 g of the resulting material (1-butoxy-3- (2-methylaziridin-1-yl) propan-2-ol) and 28.63 g of 1- (2-methylaziridin-1-yl) propan-2-ol were charged together with 0.02 g of bismuth neodecanoate and 32.54 g of 2-methyltetrahydrofuran in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 100 grams Desmodur N3600 in 32.54 grams 2-methyltetrahydrofuran was then added dropwise over 45 minutes to the reaction flask, 10 grams 2-methyltetrahydrofuran was flushed into the reaction mixture through the feed funnel, and the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a pale yellow high viscosity liquid. The calculated molecular weight of the theoretical principal component is 84957Da (three methyl side groups), 921.63Da (two methyl side groups, one butoxymethyl side group), 993.68Da (one methyl side group, two butoxymethyl side groups), and 1065.74Da (three butoxymethyl side groups), the chemical structures are shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =872.57Da; observed [ M + Na + ] =872.59Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =944.63Da; observed [ M + Na + ] =944.66Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1016.68Da; observed [ M + Na + ] =1016.72Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1088.74Da; observed [ M + Na + ] =1088.79Da.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.74 parts of the composition was mixed with 0.74 parts of 1-methoxy-2-propyl acetate and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 15 parts under continuous stirring

R-1005 and the resulting mixture is stirred furtherStirring for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 10-1). For reference, films were also cast from the same composition lacking the crosslinker (test 10-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Comparative example 10

A1L round bottom flask equipped with a condenser was placed in N ₂ Under atmosphere, charged with propyleneimine (80.0 g), n-butyl glycidyl ether (126.0 g) and K ₂ CO ₃ (10.00 g) and heated to 80 ℃ over 30 minutes, after which the mixture was stirred at T =80 ℃ for 21 hours. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

20.9 g of the resulting material (1-butoxy-3- (2-methylaziridin-1-yl) propan-2-ol) were charged together with 0.02 g of bismuth neodecanoate in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. 10.0 g of HDI were then added dropwise to the reaction flask over 30 minutes, and the mixture was then heated further to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer. After 3 hours, 0.25g of 1-butanol was added to the reaction mixture and the mixture was stirred at 80 ℃ for 1 hour. After cooling to room temperature, a yellowish highly viscous liquid was obtained. The calculated molecular weight of the theoretical main component is 542.40Da, and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =565.40Da; observed [ M + Na + ] =565.49Da.

Genotoxicity test

Comparative example 11

20.2 g of the resulting material (1-butoxy-3- (2-methylaziridin-1-yl) propan-2-ol) were charged together with 0.02 g of bismuth neodecanoate in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. Then 10.0 g of TDI was added dropwise over 30 minutes to the reaction flask, and the mixture was further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. After cooling to room temperature, an opaque solid was obtained. The calculated molecular weight of the theoretical main component is 548.36Da, and the chemical structure is as followsShown in the figure.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =571.36Da; observed [ M + Na + ] =571.42Da.

Genotoxicity test

Example 11

Place 1L round bottom flask equipped with condenser in N ₂ Under atmosphere, charged with propyleneimine (80.0 g), n-butyl glycidyl ether (126.0 g) and K ₂ CO ₃ (10.00 g) and heated to 80 ℃ over 30 minutes, after which the mixture was stirred at T =80 ℃ for 21 hours. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

8.72 g of the resulting material (1-butoxy-3- (2-methylaziridin-1-yl) propan-2-ol) were charged into a reaction flask equipped with a thermometer, along with 0.02 g of bismuth neodecanoate and 24.85 g of 2-methyltetrahydrofuran. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 6.0 g of 1, 3-bis (1-isocyanato-1-methylethyl) benzene in 24.85 g of 2-methyltetrahydrofuran is then added dropwise over 45 minutes to the reaction flask, and the mixture is then heated further to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 Until no change in NCO elongation was observed. Subsequently, 0.18 g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above-mentioned NCO stretching peak. The solvent was removed in vacuo to obtain a dark yellow, high viscosity, translucent liquid. The calculated molecular weight of the theoretical main component is 618.44Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =641.44Da; observed [ M + Na + ] =641.44Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present in the composition at 0.2 wt%.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.16 parts of the composition was mixed with 0.16 parts of 1-methoxy-2-propyl acetate and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 5 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 11-1). For reference, films were also cast from the same composition lacking the crosslinker (test 11-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 12

Place 1L round bottom flask equipped with condenser in N ₂ Under atmosphere, and charged with propyleneimine (80.0 g), n-butyl glycidyl ether (126.0 g) and K ₂ CO ₃ (10.00 g) and heated to 80 ℃ over 30 minutes, after which the mixture was stirred at T =80 ℃ for 21 hours. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

8.12 g of the resulting material (1-butoxy-3- (2-methylaziridin-1-yl) propan-2-ol) were charged with 0.02 g of bismuth neodecanoate and 23.62 g of 2-methyltetrahydrofuran in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 6.0 g of 4,4' -methylenebis (cyclohexyl isocyanate) in 23.62 g of 2-methyltetrahydrofuran was then added dropwise over 45 minutes to the reaction flask, and the mixture was further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 Until no change in NCO elongation was observed. Subsequently, 0.17 g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above-mentioned NCO stretching peak. The solvent was removed in vacuo to obtain a pale yellow, highly viscous, translucent liquid. The calculated molecular weight of the theoretical main component is 636.48Da, and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =659.48Da; observed [ M + Na + ] =659.47Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present at 0.04 wt% in the composition.

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 12-1). For reference, films were also cast from the same composition lacking the crosslinker (test 12-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 13

A1L round bottom flask equipped with a condenser was placed in N ₂ Under an atmosphere, charged with propyleneimine (80.0 g), n-butyl glycidyl ether (126.0 g)G) and K ₂ CO ₃ (10.00 g) and heated to 80 ℃ over 30 minutes, after which the mixture was stirred at T =80 ℃ for 21 hours. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

20 grams of Desmodur N3400 and 0.02 grams of bismuth neodecanoate were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. 17.88 g of the product from the first step were then added dropwise over 10 minutes to the reaction flask, and the mixture was then further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 No change in NCO elongation was observed. Subsequently, 0.16 g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above-mentioned NCO stretching peak. The product was a yellowish high viscosity liquid. The calculated molecular weight of the theoretical main component is 710.49Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =733.49Da; observed [ M + Na + ] =733.57Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.2% by weight, and

present at less than 0.01 wt%.

Genotoxicity test

Example 14

1.92 g of the resulting material (1-butoxy-3- (2-methylaziridin-1-yl) propan-2-ol) were charged together with 0.02 g of bismuth neodecanoate and 19 g of dimethylformamide into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 2.00 grams Desmodur N3600 in 19 grams dimethylformamide was then added dropwise over 45 minutes to the reaction flask, after which the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear, pale yellow, high viscosity liquid. The calculated molecular weight of the theoretical main component is 1065.74Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1088.74Da; observed [ M + Na + ] =1088.76Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.36% by weight, and

present at less than 0.01 wt%.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.58 parts of the composition was mixed with 0.60 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.79 part of the resulting solution was added to 20 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 14-1). For reference, films were also cast from the same composition lacking the crosslinker (test 14-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Example 15

26.98 g of the resulting material (1-butoxy-3- (2-methylaziridin-1-yl) propan-2-ol) were charged into a reaction flask equipped with a thermometer along with 0.02 g of bismuth neodecanoate and 6.79 g of 2-methyltetrahydrofuran. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 28.00 g Desmodur N3900 in 6.79 g 2-methyltetrahydrofuran was then added dropwise over 45 minutes to the reaction flask, 10 g 2-methyltetrahydrofuran were flushed into the reaction mixture through the feed funnel, and the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear, pale yellow, high viscosity liquid. The calculated molecular weight of the theoretical main component is 1065.74Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1088.74Da; observed [ M + Na + ] =1088.81Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.30% by weight, and

present at 0.02 wt%.

Genotoxicity testing

Example 16

20 grams of Desmodur XP2860 and 0.02 grams of bismuth neodecanoate were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. 16.40 grams of the product from the first step was then added dropwise over 10 minutes to the reaction flask, and the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 Until no change in NCO elongation was observed. Subsequently, 0.16 g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above-mentioned NCO stretching peak. The product was a pale yellow, translucent, high viscosity liquid. The theoretical calculated molecular weights of the main components are 770.55Da (propyl side groups), 784.57Da (butyl side groups) and 798.58Da (pentyl side groups), and the chemical structures are shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =793.55Da; observed [ M + Na + ] =793.57Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =807.57Da; observed [ M + Na + ] =807.61Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =821.58Da; observed [ M + Na + ] =821.63Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.66 wt.% and

present at 0.14 wt%.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.62 parts of the composition was mixed with 0.62 parts of 1-methoxy-2-propyl acetate and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 15 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 16-1). For reference, films were also cast from the same composition lacking the crosslinker (test 16-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Example 17

18.21 g of the resulting material (1-butoxy-3- (2-methylaziridin-1-yl) propan-2-ol) and 9.45 g of poly (ethylene glycol) monomethyl ether having an average Mn of 350Da were charged together with 0.02 g of bismuth neodecanoate and 6.29 g of 2-methyltetrahydrofuran in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 25.0 grams Desmodur N3600 in 6.29 grams 2-methyltetrahydrofuran was then added dropwise over 25 minutes to the reaction flask, 10 grams 2-methyltetrahydrofuran was flushed into the reaction mixture through the feed funnel, and the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a pale yellow, highly viscous, translucent liquid. The calculated molecular weights of the theoretical main components are 1065.74Da (three aziridines), 1218.79Da (two aziridines, 7EG repeat units), 1262.82Da (two aziridines, 8EG repeat units), and 1306.85Da (two aziridines, 9EG repeat units), with the chemical structures shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1088.74Da; observed [ M + Na + ] =1088.90Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1241.79Da; observed [ M + Na + ] =1241.96Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1285.82Da; observed [ M + Na + ] =1286.00Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1329.85Da; observed [ M + Na + ] =1330.03Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.03% by weight, and

present at less than 0.01 wt%.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.98 parts of the composition is mixed with 025 parts of 1-methoxy-2-propyl acetate are mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 15 parts under continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 17-1). For reference, films were also cast from the same composition lacking the crosslinker (test 17-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 18

49.5 g of the resulting material (1-butoxy-3- (2-methylaziridin-1-yl) propan-2-ol) were reacted with 35.2 g of poly (ethylene glycol) monomethyl ether having an average Mn of 500Da, 0.2 g of bismuth neodecanoate and 425 g of dimethylmethaneThe amides were charged together in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 65.2 grams Desmodur N3600 in 425 grams dimethylformamide was then added dropwise over 45 minutes to the reaction flask, after which the mixture was further heated to 75 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear, dark yellow, high viscosity liquid. The calculated molecular weights of the theoretical main components are 1065.74Da (three aziridines), 1394.90Da (two aziridines, 11EG repeat units), 1438.92Da (two aziridines, 12EG repeat units) and 1482.95Da (two aziridines, 13EG repeat units), with the chemical structures shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1088.74Da; observed [ M + Na + ] =1088.67Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1417.90Da; observed [ M + Na + ] =1417.81Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1461.92Da; observed [ M + Na + ] =1461.84Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1505.95Da; observed [ M + Na + ] =1505.86Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.04% by weight, and

present at 0.05 wt%.

The properties of the synthesized compounds as crosslinkers were assessed using the spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.83 parts of the composition was mixed with 0.60 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.95 part of the resulting solution was added to 20 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 18-1). For reference, films were also cast from the same composition lacking the crosslinker (test 18-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

For demonstration purposes, the mutagenicity of the crosslinker compositions was also assessed using the established Ames test (bacterial regression assay) according to the following guidelines:

OECD guideline 471. Genetic toxicology: and (3) testing reverse mutation of bacteria. (passage on 21/7/1997).

EC guide number 440/2008. And part B: method for determining toxicity and other health effects, guideline b.13/14: the mutagenicity: reverse mutation test using bacteria ", eu official gazette No. L142, 2008, 5 months and 31 days.

This test shows that the crosslinker composition as described above is not mutagenic.

Example 19

A 20mL reaction vial was charged with propyleneimine (2.97 g), cyclohexene oxide (4.06 g), capped, heated to 55 ℃, after which the mixture was stirred at T =55 ℃ for 8 days. Excess PI was removed in vacuo, followed by further purification by vacuum distillation to give a white powder.

2.00 grams Desmodur N3600, 0.02 grams bismuth neodecanoate, and 3.60 grams dimethylformamide were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 1.54 grams of the product from the first step in 3.60 grams of dimethylformamide was then added dropwise over 10 minutes to the reaction flask, 3.60 grams of dimethylformamide was flushed into the reaction mixture through the feed funnel, and the mixture was further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No change in NCO elongation was observed. Subsequently, 0.06 g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above-mentioned NCO stretching peak. The product was a slightly opaque liquid. The theoretical main component has a calculated molecular weight of 969.66Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =992.66Da; observed [ M + Na + ] =992.77Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.27% by weight, and

present at less than 0.01 wt%.

The properties of the synthesized compounds as crosslinkers were assessed using the spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 2.01 parts of the composition (i.e. at 25% solids in dimethylformamide) were added to 15 parts with continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 19-1). For reference, films were also cast from the same composition lacking the crosslinker (test 19-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 20

A1L round bottom flask equipped with a condenser was placed in N ₂ Under atmosphere, charged with propyleneimine (91.0 g), 2-ethylhexyl glycidyl ether (201.0 g) and K ₂ CO ₃ (10.00 g) and heated to 80 ℃, after which the mixture was stirred at T =80 ℃ for 47 hours. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

130 g of the resulting material were charged together with 0.02 g of bismuth neodecanoate and 668 g of dimethylformamide into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 107.4 grams Desmodur N3600 in 668 grams dimethylformamide was then added dropwise over 45 minutes to the reaction flask, 10 grams dimethylformamide was flushed into the reaction mixture through the feed funnel, and the mixture was further heated to 75 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a high viscosity colorless liquid. The calculated molecular weight of the theoretical main component is 1233.93Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1256.93Da; observed [ M + Na + ] =1256.86Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.84% by weight, and

present at 0.16 wt%.

The properties of the synthesized compounds as crosslinkers were assessed using the spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.96 parts of the composition was mixed with 0.96 parts of 1-methoxy-2-propyl acetate and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 15 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 20-1). For reference, films were also cast from the same composition lacking the crosslinker (test 20-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Example 21

A 20mL reaction vial was charged with propyleneimine (1.98 g), o-toluene glycidyl ether (5.57 g), capped, heated to 55 ℃, after which the mixture was stirred at T =55 ℃ for 20 hours. Excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

0.90 grams Desmodur N3600, 0.02 grams bismuth neodecanoate, and 5.80 grams dimethylformamide were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 0.99 grams of the product from the first step in 5.80 grams of dimethylformamide was then added dropwise over a period of 5 minutes to the reaction flask, and 5.80 grams of dimethylformamide was flushed into the reaction mixture through the feed funnel, and the mixture was then further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was evaporated in vacuo to 43% solids to give a low viscosity pale yellow liquid. The calculated molecular weight of the theoretical main component is 1167.69Da, and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1190.69Da; observed [ M + Na + ] =1190.77Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition at 0.08% by weight, and

present at 0.08 wt%.

Based on signals from DIN 68861-1Standard procedures spot tests on the coated surface were used to assess the performance of the synthesized compounds as crosslinkers. For these tests, 0.47 parts of the composition (i.e. at 43% solids in dimethylformamide) was added to 5 parts with continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 21-1). For reference, films were also cast from the same composition lacking the crosslinker (test 21-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Example 22

A1L round bottom flask equipped with a condenser was placed in N ₂ Under an atmosphere, charged with propyleneimine (69.0 g), cardura E10P (201.0 g) and K ₂ CO ₃ (7.30 g) and heated to 80 ℃, after which the mixture was stirred at T =80 ℃ for 24 hours. After filtration, excess PI was removed in vacuo to give a colorless, low viscosity liquid.

11.09 g of the resulting material (2-hydroxy-3- (2-methylaziridin-1-yl) propyl neodecanoate) was charged together with 0.02 g of bismuth neodecanoate and 46 g of dimethylformamide into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 5.00 g of 1, 3-bis (1-isocyanato-1-methylethyl) benzene in 46 g of dimethylformamide is then added dropwise over 45 minutes to the reaction flask, after which the mixture is further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain an opaque viscous liquid. The calculated molecular weight of the theoretical main component is 814.58Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =837.58Da; observed [ M + Na + ] =837.48Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present at 1.3 wt% in the composition.

The properties of the synthesized compounds as crosslinkers were assessed using the spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.61 part of the composition was mixed with 0.60 part of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.81 part of the resulting solution was added to 20 parts under continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. Then, the coating composition was filtered, and 1 was usedA00 μm wire coater was applied to a Leneta test card (test 22-1). For reference, films were also cast from the same composition lacking the crosslinker (test 22-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Example 23

A1L round bottom flask equipped with a condenser was placed in N ₂ Under an atmosphere, and charged with propyleneimine (69.0 g), cardura E10P (201.0 g) and K ₂ CO ₃ (7.30 g) and heated to 80 ℃, after which the mixture was stirred at T =80 ℃ for 24 hours. After filtration, excess PI was removed in vacuo to give a colorless, low viscosity liquid.

10.33 g of the resulting material (2-hydroxy-3- (2-methylaziridin-1-yl) propyl neodecanoate) were charged together with 0.02 g of bismuth neodecanoate and 43 g of dimethylformamide into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 5.00 grams of 4,4' -methylenebis (cyclohexyl isocyanate) in 43 grams of dimethylformamide was then added dropwise over 45 minutes to the reaction flask, after which the mixture was further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. Removing the solvent in vacuo to obtain opacityThe viscous liquid of (2). The calculated molecular weight of the theoretical main component is 832.63Da, and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =855.62Da; observed [ M + Na + ] =855.52Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present in the composition at 0.2 wt%.

The properties of the synthesized compounds as crosslinkers were assessed using the spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.64 parts of the composition was mixed with 0.60 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.83 part of the resulting solution was added to 21 parts under continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 23-1). For reference, films were also cast from the same composition lacking the crosslinker (test 23-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Example 24

2.20 g of the resulting material (2-hydroxy-3- (2-methylaziridin-1-yl) propyl neodecanoate) were charged together with 0.02 g of bismuth neodecanoate and 18 g of dimethylformamide into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 1.50 grams Desmodur N3600 in 18 grams dimethylformamide was then added dropwise over 15 minutes to the reaction flask, after which the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain an opaque high viscosity liquid. The calculated molecular weight of the theoretical main component is 1359.96Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1382.95Da; observed [ M + Na + ] =1382.86Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present at 0.27 wt% in the composition.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.68 parts of the composition was mixed with 0.60 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.86 part of the resulting solution was added to 21 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 24-1). For reference, films were also cast from the same composition lacking the crosslinker (test 24-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 25

Place 1L round bottom flask equipped with condenser in N ₂ Under an atmosphere, charged with propyleneimine (69.0 g), cardura E10P (201.0 g) and K ₂ CO ₃ (7.30 g) and heated to 80 ℃, after which the mixture was stirred at T =80 ℃ for 24 hours. After filtration, excess PI was removed in vacuo to give a colorless, low viscosity liquid.

A500 mL round-bottom flask equipped with a thermometer and an overhead stirrer was placed in N ₂ Under atmosphere, and Desmodur W (60.08 g) and 65.35 g of the product of the previous step were charged. The resulting mixture was heated to 50 ℃, after which bismuth neodecanoate (0.05 g) was added. The mixture was allowed to exotherm and then further heated to 80 ℃ and stirred at 80 ℃ for 2.5 hours. pTHF650 (74.52 g) was then added to the mixture and the mixture was stirred at 80 ℃ for a further 1 hour. The solvent was removed in vacuo to give a colorless solid.

The calculated molecular weights of the theoretical main components were 832.63Da (Structure 25-a: no pTHF650 repeat unit), 1473.1.0Da (Structure 25-b: one pTHF segment with 5 tetramethylene ether glycol repeat units), 1545.15Da (Structure 25-c: one pTHF segment with 6 tetramethylene ether glycol repeat units), and 2257.68Da (Structure 25-d: two pTHF segments with 6 tetramethylene ether glycol repeat units), the chemical structures of which are shown below.

Structure 25-a:

molecular weight was confirmed by Maldi-TOF-MS: structure 25-a: calculated [ M + Na + ] =855.63Da; observed [ M + Na + ] =855.66Da.

Structure 25-b:

molecular weight was confirmed by Maldi-TOF-MS: structure 25-b: calculated [ M + Na + ] =1496.10Da; observed [ M + Na + ] =1496.16Da.

Structure 25-c:

molecular weight was confirmed by Maldi-TOF-MS: structure 25-c: calculated [ M + Na + ] =1568.15Da; observed [ M + Na + ] =1568.21Da.

Structure 25-d:

molecular weight was confirmed by Maldi-TOF-MS: structure 25-d: calculated [ M + Na + ] =2280.68Da; observed [ M + Na + ] =2280.78Da.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 1.36 parts of the composition was mixed with 1.36 parts of 1-methoxy-2-propyl acetate and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 15 parts under continuous stirring

R-1005, and the resulting mixture is stirred for a further 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 25-1). For reference, films were also cast from the same composition lacking the crosslinker (test 25-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 26

Place a 500mL round-bottom flask equipped with a thermometer and overhead stirrer into N ₂ Under atmosphere, and Desmodur W (49.60 g) and 53.95 g of the product of the previous step were charged. The resulting mixture was heated to 50 ℃, after which bismuth neodecanoate (0.04 g) was added. The mixture was allowed to exotherm then heated further to 80 ℃ and stirred at 80 ℃ for 2 hours. To this mixture was then added Durez-ter S105-110 (96.40 g). After stirring for a further 2.5 hours at 80 ℃ a second batch of Durez-ter S105-110 (10.00 g) is added to the mixture and the mixture is stirred for a further 11 hours at 80 ℃. The solvent was removed in vacuo to obtain a white solid.

The calculated molecular weights of the theoretical main components were 832.63Da (structure 26-a), 1212.90 (structure 26-b: one hexanediol linking group between two Desmodur W groups from Durez-ter S105-110), 1441.03Da (structure 26-c:1 polyester repeating unit), 1669.17Da (structure 26-d:2 polyester repeating units), 1897.30Da (structure 26-e:3 polyester repeating units) and 2125.44Da (structure 26-f:4 polyester repeating units), the chemical structures being shown below.

Structure 26-a:

molecular weight was confirmed by Maldi-TOF-MS: structure 26-a: calculated [ M + Na + ] =855.63Da; observed [ M + Na + ] =855.70Da.

Structure 26-b:

molecular weight was confirmed by Maldi-TOF-MS: structure 26-b: calculated [ M + Na + ] =1235.90Da; observed [ M + Na + ] =1236.01Da.

Structure 26-c:

molecular weight was confirmed by Maldi-TOF-MS: structure 26-c: calculated [ M + Na + ] =1464.03Da; observed [ M + Na + ] =1464.16Da.

Structure 26-d:

molecular weight was confirmed by Maldi-TOF-MS: structure 26-d: calculated [ M + Na + ] =1692.17Da; observed [ M + Na + ] =1692.32Da.

Structure 26-e:

molecular weight was confirmed by Maldi-TOF-MS: structure 26-e: calculated [ M + Na + ] =1920.30Da; observed [ M + Na + ] =1920.48Da.

Structure 26-f:

molecular weight was confirmed by Maldi-TOF-MS: structure 26-f: calculated [ M + Na + ] =2148.44Da; observed [ M + Na + ] =2148.62Da.

The procedure based on the standard from DIN 68861-1 was used to test spots on the surface of the coatingThe properties of the synthesized compounds as a crosslinking agent were evaluated. For these tests, 1.73 parts of the composition was mixed with 1.73 parts of 1-methoxy-2-propyl acetate and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, the resulting solution was added to 15 parts under continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 26-1). For reference, films were also cast from the same composition lacking the crosslinker (test 26-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 27

2.89 g of the resulting material (2-hydroxy-3- (2-methylaziridin-1-yl) propyl neodecanoate) were mixed with 0.02 g of bismuth neodecanoate, 1.35 g of poly (ethylene glycol) having an average Mn of 500Da) Monomethyl ether and 30 grams of dimethylformamide were charged together into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 2.5 grams Desmodur N3600 in 30 grams dimethylformamide was then added dropwise over 45 minutes to the reaction flask, after which the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a clear high viscosity liquid. The calculated molecular weights of the theoretical main components are 1359.96Da (three aziridines) and 1591.04Da (two aziridines, 11EG repeat units) and the chemical structures are shown below.

The properties of the synthesized compounds as crosslinkers were assessed using a spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.93 parts of the composition was combined with 0.60 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 1.02 parts of the resulting solution was added to 20 parts under continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 27-1). For reference, films were also cast from the same composition lacking the crosslinker (test 27-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity testing

Example 28

19.49 g of the resulting material (2-hydroxy-3- (2-methylaziridin-1-yl) propyl neodecanoate) were charged together with 0.02 g of bismuth neodecanoate, 37.94 g of poly (ethylene glycol) monomethyl ether having an average Mn of 2000Da and 11.07 g of 2-methyltetrahydrofuran in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 17.55 grams Desmodur N3600 in 11.07 grams 2-methyltetrahydrofuran was then added dropwise over 45 minutes to the reaction flask, 10 grams 2-methyltetrahydrofuran was flushed into the reaction mixture through the feed funnel, and the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain an opaque high viscosity liquid. The calculated molecular weights of the theoretical main components were 1359.96Da (three aziridines), 3043.91Da (two aziridines, 44EG repeat units), 3087.94Da (two aziridines, 45EG repeat units) and 3131.96Da (two aziridines, 46EG repeat units), esterifiedThe chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1382.96Da; observed [ M + Na + ] =1382.91Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =3066.91Da; observed [ M + Na + ] =3066.77Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =3110.94Da; observed [ M + Na + ] =3110.79Da.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =3154.96Da; observed [ M + Na + ] =3154.81Da. The following components with masses below 580Da were determined and quantified by LC-MS:

present at 0.02 wt% in the composition.

Genotoxicity testing

Example 29

100mL of a reaction vessel equipped with a condenserReactor is arranged at N ₂ Under atmosphere and charged propyleneimine (2.40 g), mPEG-epoxide with MW of 550Da (10.1 g), 2-methyltetrahydrofuran (20 mL) and K ₂ CO ₃ (1.1 g) and heated to 80 ℃ then the mixture was stirred at T =80 ℃ for 25 hours. After filtration, the solvent and excess PI were removed in vacuo to give a dark brown viscous oil.

3.57 g of the resulting material (1- (. Omega. -methoxy (oligoethylene oxide)) -3- (2-methylaziridin-1-yl) propan-2-ol with a MW of 550 Da) were charged together with 0.02 g of bismuth neodecanoate and 21 g of dimethylformamide to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 1.00 grams Desmodur N3600 in 21 grams dimethylformamide was then added dropwise over 15 minutes to the reaction flask, after which the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. The solvent was removed in vacuo to obtain a brown high viscosity liquid. The calculated molecular weight of the theoretical main component is 2656.62Da and the chemical structure is shown below.

The properties of the synthesized compounds as crosslinkers were assessed using the spot test on the coating surface based on the procedure from DIN 68861-1 standard. For these tests, 0.70 parts of the composition is combined with 0.39 parts of Proglyde ^TM DMM (dipropylene glycol dimethyl ether, mixture of isomers) was mixed and incubated at 80 ℃ for 10 minutes with regular stirring. Subsequently, 0.73 part of the resulting solution was added to 20 parts under continuous stirring

R-1005, and the resulting mixture was further stirred for 30 minutes. The coating composition was then filtered and applied to a Leneta test card using a 100 μm wire coater (test 29-1). As a reference, the same composition lacking the crosslinking agent was also preparedFilm casting (test 29-2). The film was dried at 25 ℃ for 16 hours, then annealed at 50 ℃ for 1 hour, and further dried at 25 ℃ for 24 hours. Subsequently, a piece of absorbent cotton was immersed in 1. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the membrane, 10 indicates no visible damage):

ethanol spot test

Genotoxicity test

Example 30

A100 mL reactor equipped with a condenser was placed in N ₂ Under atmosphere and charged with propyleneimine (1.30 g), mPEG-epoxide of MW 1kDa (10.1 g), 2-methyltetrahydrofuran (50 mL) and K ₂ CO ₃ (1.1 g) and heated to 80 ℃ then the mixture was stirred at T =80 ℃ for 25 hours. After filtration, the solvent and excess PI were removed in vacuo to give a light brown viscous liquid.

5.61 g of the resulting material (1- (. Omega. -methoxy (oligoethylene oxide)) -3- (2-methylaziridin-1-yl) propan-2-ol with MW 1 kDa) were charged together with 0.02 g of bismuth neodecanoate and 13.79 g of 2-methyltetrahydrofuran in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 1.00 grams Desmodur N3600 in 13.79 grams 2-methyltetrahydrofuran was then added dropwise over 25 minutes to the reaction flask, 10 grams 2-methyltetrahydrofuran was flushed into the reaction mixture through the feed funnel, and the mixture was further heated to 70 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 No NCO stretching was observed. Vacuum removalSolvent to obtain a brown high viscosity liquid. The calculated molecular weight of the theoretical main component is 4241.57Da, and the chemical structure is shown below.

Genotoxicity testing

Example 31

A100 mL reactor equipped with a condenser was placed in N ₂ Under an atmosphere, and 2, 2-dimethyl aziridine (8.00 g), n-butyl glycidyl ether (10.0 g), 2-methyltetrahydrofuran (20 mL) and K ₂ CO ₃ (0.75 g) and heated to 80 ℃ over 30 minutes, then the mixture was stirred at T =80 ℃ for 44 hours. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

0.26 g of the resulting material (1-butoxy-3- (2, 2-dimethylaziridin-1-yl) propan-2-ol) was charged into a reaction flask equipped with a thermometer, along with 0.01 g of bismuth neodecanoate and 3g of dimethylformamide. The mixture was stirred with a mechanical overhead stirrer under nitrogen and heated to 50 ℃. A solution of 0.26 grams Desmodur N3600 in 3 grams dimethylformamide was then added dropwise over 10 minutes to the reaction flask, 1 gram of dimethylformamide was flushed into the reaction mixture through the feed funnel, and the mixture was further heated to 80 ℃. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200 to 2300cm ^-1 No change in NCO elongation was observed. Subsequently, 0.03g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above-mentioned NCO stretching peak. The mixture was an opaque liquid. The calculated molecular weight of the theoretical main component was 1107.79Da and the chemical structure is shown below.

Molecular weight was confirmed by Maldi-TOF-MS: calculated [ M + Na + ] =1130.79Da; observed [ M + Na + ] =1130.86Da. The following components with masses below 580Da were determined and quantified by LC-MS:

is present in the composition in an amount of less than 0.01% by weight and

present at 0.89% by weight in the composition.

Genotoxicity testing

Example 32

A reaction vial was charged with 2-ethyl aziridine (2.50 g), n-butyl glycidyl ether (2.00 g) and K ₂ CO ₃ (0.5 g), capped and heated to 80 ℃, then the mixture was stirred at T =80 ℃ for 20 hours. After filtration, excess PI was removed in vacuo before further purification by vacuum distillation to give a colorless, low viscosity liquid.

4.0 grams of Desmodur N3600, 0.02 grams of bismuth neodecanoate and 8.10 grams of dimethylformamide were charged to a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under nitrogen atmosphere and heated to 50 ℃. A solution of 4.0 grams of the product from the first step in 8.10 grams of dimethylformamide was then added dropwise over 10 minutes to the reaction flask, and 8.10 grams of dimethylformamide was flushed into the reaction mixture through the feed funnel, and the mixture was then further heated to 80 ℃. Sampling at regular intervals, anThe progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until 2200-2300cm ^-1 Until no change in NCO elongation was observed. Subsequently, 0.13 g of 1-butanol was added to the mixture, followed by further reaction to completely disappear the above-mentioned NCO stretching peak. The mixture was a clear liquid. The calculated molecular weight of the theoretical main component was 1107.79Da and the chemical structure is shown below.

Genotoxicity test

Claims

1. A polyaziridine compound having:

a) 2 to 6 of the following structural units (a):

（A）

wherein

R ₁ Is H;

R ₂ and R ₄ Independently selected from H, a linear group containing from 1 to 8 carbon atoms and optionally containing one or more heteroatoms, a branched or cyclic group containing from 3 to 8 carbon atoms and optionally containing one or more heteroatoms, phenyl, benzyl or pyridyl;

R ₃ is a linear group containing from 1 to 8 carbon atoms and optionally containing one or more heteroatoms, a branched or cyclic group containing from 3 to 8 carbon atoms and optionally containing one or more heteroatoms, a phenyl, benzyl or pyridyl group;

or at R ₂ In the case of being different from H, R ₂ And R ₃ May be part of the same cyclic group containing from 3 to 8 carbon atoms;

r' is H or an alkyl group containing 1 to 12 carbon atoms, and

r' is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, CH ₂ -O-(C=O)-R'''、CH ₂ -O-R '' '' or CH ₂ -(OCR'''''HCR'''''H) _n -OR "' ', wherein R" ' is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R "' ' is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms OR an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R" ' ' is independently H OR an aliphatic hydrocarbon group containing 1 to 12 carbon atoms, and R "' ' is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms;

or R ' and R ' ' may be part of the same saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms;

m is an integer of 1 to 6;

b) One or more connecting chains, wherein each of these connecting chains connects two of the structural units a, and the connecting chain is the shortest chain of consecutive atoms connecting two structural units a; and

c) Molecular weights in the range of 600 daltons to 5000 daltons, measured using MALDI-TOF mass spectrometry.

2. The polyethylenimine compound of claim 1, wherein R ₂ And R ₄ Independently selected from H or aliphatic hydrocarbyl groups containing 1 to 2 carbon atoms, and R ₃ Is an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

3. The polyaziridine compound of claim 1, wherein R ₂ Is H, R ₃ Is CH ₃ And R is ₄ Is H.

4. The polyaziridine compound of claim 1, wherein R ₂ Is H, R ₃ Is CH ₃ And R is ₄ Is CH ₃ 。

5. The polyethylenimine compound of claim 1, wherein R' is H or an alkyl group containing 1 to 4 carbon atoms.

6. The polyaziridine compound of claim 1, wherein R' is H or alkyl containing 1 to 2 carbon atoms.

7. The polyethylenimine compound of claim 1, wherein m is 1.

8. The polyethylenimine compound of claim 1, wherein

R' = H or alkyl group containing 1 to 2 carbon atoms;

r' = aliphatic hydrocarbon group containing 1 to 4 carbon atoms, CH ₂ -O-(C=O)-R'''、CH ₂ -O-R '' '' or CH ₂ -(OCR'''''HCR'''''H) _n -OR ' ' ' ' ' ' ', wherein R ' ' ' is an alkyl group containing 1 to 12 carbon atoms and R ' ' ' ' is an alkyl group containing 1 to 12 carbon atoms, n is 1 to 35, R ' ' ' ' is independently H OR methyl, and R ' ' ' ' ' is an alkyl group containing 1 to 4 carbon atoms;

m is 1.

9. The polyaziridine compound of claim 1, wherein R' is H and R "= alkyl containing 1 to 4 carbon atoms, CH ₂ -O-(C=O)-R'''、CH ₂ -O-R '' '' or CH ₂ -(OCH ₂ CH ₂ ) _n -OCH ₃ Wherein R '' 'is an alkyl group having 3 to 12 carbon atoms and R' '' is an alkyl group having 1 to 12 carbon atoms.

10. The polyaziridine compound of claim 1, wherein the polyaziridine compound contains 2 or 3 structural units (a).

11. The polyaziridine compound of claim 1, wherein the connecting chain consists of 6 to 100 atoms, and the atoms of the connecting chain are C, N, and/or O.

12. The polyethylenimine compound of claim 1, wherein the molecular weight of the polyethylenimine compound is from 840 daltons to 3800 daltons.

13. The polyethylenimine compound according to claim 1, wherein the polyethylenimine compound comprises one or more linking groups, wherein each of these linking groups connects two of said structural units a, wherein a linking group is defined as an array of consecutive functional groups connecting two structural units a, and wherein the linking group consists of at least one functional group selected from the group consisting of: aliphatic hydrocarbon functional groups, alicyclic hydrocarbon functional groups, aromatic hydrocarbon functional groups, isocyanurate functional groups, iminooxadiazinedione functional groups, ether functional groups, ester functional groups, amide functional groups, carbonate functional groups, carbamate functional groups, urea functional groups, biuret functional groups, allophanate functional groups, uretdione functional groups, and any combination thereof.

14. The polyethylenimine compound according to claim 1, wherein the polyethylenimine compound comprises one or more linking groups, wherein each of these linking groups connects two of said structural units a, wherein a linking group is defined as an array of consecutive functional groups connecting two structural units a, and wherein said linking group consists of at least one functional group selected from the group consisting of: aliphatic hydrocarbon functional groups, alicyclic hydrocarbon functional groups, aromatic hydrocarbon functional groups, isocyanurate functional groups, iminooxadiazinedione functional groups, carbamate functional groups, urea functional groups, biuret functional groups, and any combination thereof.

15. The polyethylenimine compound according to claim 1, wherein the polyethylenimine compound comprises one or more linking groups, wherein each of these linking groups connects two of said structural units A, wherein a linking group is defined as an array of consecutive functional groups connecting two structural units A, and wherein said linking group consists of at least one aliphatic hydrocarbon functional group and/or at least one alicyclic hydrocarbon functional group and optionally at least one aromatic hydrocarbon functional group and optionally an isocyanurate functional group or an iminooxadiazinedione functional group.

16. The polyaziridine compound of any of claims 2-6 and 8-15, wherein m is 1.

17. The polyaziridine compound according to any one of claims 2-7 and 9-15, wherein

R' = H or alkyl group containing 1 to 2 carbon atoms;

r' = aliphatic hydrocarbon group containing 1 to 4 carbon atoms, CH ₂ -O-(C=O)-R'''、CH ₂ -O-R '' '' or CH ₂ -(OCR'''''HCR'''''H) _n -OR "'' ', wherein R"' is an alkyl group containing from 1 to 12 carbon atoms and R "'' is an alkyl group containing from 1 to 12 carbon atoms, n is from 1 to 35, R" '' 'is independently H OR methyl, and R "' '' is an alkyl group containing from 1 to 4 carbon atoms;

or R ' and R ' ' may be part of the same saturated cycloaliphatic hydrocarbon group containing from 5 to 8 carbon atoms;

m is 1.

18. The polyethylenimine compound according to any of claims 2 to 8 and 10 to 15, wherein R' is H, and R "= alkyl containing 1 to 4 carbon atoms, CH ₂ -O-(C=O)-R'''、CH ₂ -O-R '' '' or CH ₂ -(OCH ₂ CH ₂ ) _n -OCH ₃ Wherein R '' 'is an alkyl group having 3 to 12 carbon atoms and R' '' is an alkyl group having 1 to 12 carbon atoms.

19. The polyaziridine compound of any of claims 2-9 and 11-15, wherein the polyaziridine compound contains 2 or 3 structural units (a).

20. The polyethylenimine compound of any of claims 2 to 10 and 12 to 15, wherein the connecting chain consists of 6 to 100 atoms, and the atoms of the connecting chain are C, N, and/or O.

21. The polyethylenimine compound of any of claims 2 to 11 and 13 to 15, wherein the molecular weight of the polyethylenimine compound is from 840 daltons to 3800 daltons.

22. The polyethylenimine compound according to any one of claims 2 to 12 and 14 to 15, wherein the polyethylenimine compound comprises one or more linking groups, wherein each of these linking groups connects two of the structural units a, wherein a linking group is defined as an array of consecutive functional groups connecting two structural units a, and wherein the linking group consists of at least one functional group selected from: aliphatic hydrocarbon functional groups, alicyclic hydrocarbon functional groups, aromatic hydrocarbon functional groups, isocyanurate functional groups, iminooxadiazinedione functional groups, ether functional groups, ester functional groups, amide functional groups, carbonate functional groups, carbamate functional groups, urea functional groups, biuret functional groups, allophanate functional groups, uretdione functional groups, and any combination thereof.

23. The polyethylenimine compound according to any one of claims 2 to 13 and 15, wherein the polyethylenimine compound comprises one or more linking groups, wherein each of these linking groups connects two structural units a of said structural unit a, wherein a linking group is defined as an array of consecutive functional groups connecting two structural units a, and wherein the linking group of the polyethylenimine compound consists of at least one functional group selected from the group consisting of: aliphatic hydrocarbon functional groups, alicyclic hydrocarbon functional groups, aromatic hydrocarbon functional groups, isocyanurate functional groups, iminooxadiazinedione functional groups, carbamate functional groups, urea functional groups, biuret functional groups, and any combination thereof.

24. The polyethylenimine compound according to any one of claims 2 to 14, wherein the polyethylenimine compound comprises one or more linking groups, wherein each of these linking groups connects two of the structural units a, wherein a linking group is defined as an array of consecutive functional groups connecting two structural units a, and wherein the linking group consists of at least one aliphatic hydrocarbon functional group and/or at least one cycloaliphatic hydrocarbon functional group and optionally at least one aromatic hydrocarbon functional group and optionally an isocyanurate functional group or an iminooxadiazinedione functional group.

25. The polyethylenimine compound according to any one of claims 1 to 15, wherein the polyethylenimine compound comprises one or more linking groups, wherein each of these linking groups connects two of the structural units a, wherein a linking group is defined as an array of consecutive functional groups connecting two structural units a, and wherein the linking group consists of at least one aliphatic hydrocarbon functional group and/or at least one cycloaliphatic hydrocarbon functional group and an isocyanurate functional group or an iminooxadiazinedione functional group.

26. The polyethylenimine compound according to any one of claims 1 to 15, wherein the polyethylenimine compound is according to the following structural formula:

wherein Z is a molecular residue obtained by removing an isocyanate-reactive group XH of a molecule;

q is an integer of 2 to 6;

i is an integer from 1 to q;

D _i independently have the following structural formula

j is an integer from 1 to p;

p is an integer of 0 to 10,

m、R'、R''、R ₁ 、R ₂ 、R ₃ and R ₄ As defined in any one of the preceding claims.

27. The polyethylenimine compound according to any one of claims 1 to 15, wherein the polyethylenimine compound is according to the following structural formula:

wherein Z is a molecular residue obtained by removing isocyanate-reactive groups XH of a molecule and the molecule from which the isocyanate-reactive groups are removed to obtain Z is a diol, triol, polyether having terminal isocyanate-reactive groups, polyamide having terminal isocyanate-reactive groups, polycarbonate having terminal isocyanate-reactive groups, or polysiloxane having terminal isocyanate-reactive groups, the terminal isocyanate-reactive groups in the polysiloxane having terminal isocyanate-reactive groups being attached to the siloxane by at least one carbon atom,

q is an integer of 2 to 6;

i is an integer from 1 to q;

D _i independently have the formula

j is an integer from 1 to p;

p is an integer of 0 to 10 and,

28. The polyethylenimine compound according to any one of claims 1 to 15, wherein the polyethylenimine compound is according to the following structural formula:

wherein Z is a molecular residue obtained by removing an isocyanate-reactive group XH of a molecule and the molecule from which the isocyanate-reactive group is removed to obtain Z is a diol, triol, polyether having a terminal isocyanate-reactive group, polyamide having a terminal isocyanate-reactive group, polycarbonate having a terminal isocyanate-reactive group, or polysiloxane having a terminal isocyanate-reactive group, the terminal isocyanate-reactive group in the polysiloxane having a terminal isocyanate-reactive group being attached to the siloxane by at least one carbon atom,

q is an integer of 2 to 6;

i is an integer from 1 to q;

D _i independently have the formula

j is an integer from 1 to p;

p is 0 and m is 1,

R'、R''、R ₁ 、R ₂ 、R ₃ and R ₄ As defined in any one of the preceding claims.

29. The polyaziridine compound of any of claims 1-15, wherein the polyaziridine compound contains at least 5 wt% and less than 20 wt% urethane linkages.

30. The polyethylenimine compound according to any one of claims 1 to 15, wherein the polyethylenimine compound is obtained by at least reacting a polyisocyanate with compound B having the following structural formula:

，

wherein the molar ratio of compound B to polyisocyanate is from 2 to 6, and wherein m, R '', R ₁ 、R ₂ 、R ₃ And R ₄ As defined in any one of claims 1 to 16.

31. The polyaziridine compound of any of claims 1-15, wherein the polyaziridine compound is obtained by reacting at least a polyisocyanate having aliphatic reactivity with compound B having the following structural formula:

，

wherein the molar ratio of compound B to polyisocyanate is from 2 to 6, and wherein m, R '', R ₁ 、R ₂ 、R ₃ And R ₄ As defined in any one of claims 1 to 18.

32. The polyaziridine compound according to anyone of claims 1 to 15, wherein the polyaziridine compound is obtained by reacting at least a polyisocyanate having aliphatic reactivity with compound B having the following structural formula:

，

wherein the molar ratio of compound B to polyisocyanate is from 2 to 6, and wherein m, R '', R ₁ 、R ₂ 、R ₃ And R ₄ As defined in any one of claims 1 to 18,

and wherein compound B is obtained by reacting at least a non-OH functional monoepoxide compound with an aziridine having the following structural formula:

，

wherein R is ₁ 、R ₂ 、R ₃ And R ₄ As defined in any one of claims 1 to 4.

33. The polyaziridine compound of any of claims 1-15, wherein the polyaziridine compound is obtained by reacting at least a polyisocyanate having aliphatic reactivity with compound B having the following structural formula:

，

wherein the molar ratio of compound B to polyisocyanate is from 2 to 6, and wherein m, R', R ″, R ₁ 、R ₂ 、R ₃ And R ₄ As defined in any one of claims 1 to 18,

and wherein compound B is obtained by reacting at least a non-OH functional monoepoxide compound with an aziridine having the formula:

，

wherein R is ₁ 、R ₂ 、R ₃ And R ₄ As defined in any one of claims 1 to 4,

and wherein the non-OH functional monoepoxide compound is selected from the group consisting of: propylene oxide, 2-ethyloxirane, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl neodecanoate, and any mixture thereof.

34. The polyethylenimine compound of any of claims 1 to 15, wherein the polyethylenimine compound contains polyoxyethylene (-O-CH 2-) -in an amount of at least 0.1% by weight and less than 45% by weight relative to the polyethylenimine compound _x Radical or polyoxypropylene (-O-CHCH 3-CH 2-) _x Radical or polytetrahydrofuran (-O-CH 2-CH 2) _x A group.

35. A crosslinker composition comprising at least one polyaziridine compound according to any one of claims 1-15, and further comprising at least one additional component.

36. A crosslinker composition comprising at least one polyaziridine compound of any one of claims 1-15, and further comprising at least one additional component, wherein the molecular weight of polyaziridine compound of any one of claims 1-15 present in the crosslinker composition is in a range of 600 daltons to 5000 daltons.

37. A crosslinker composition comprising at least one polyaziridine compound according to any one of claims 1 to 15, and further comprising at least one additional component, wherein the amount of aziridine-functional molecules having a molecular weight of less than 580 daltons, relative to the total weight of the crosslinker composition, is less than 5 wt.%, wherein the molecular weight is determined using LC-MS.

38. A crosslinker composition comprising at least one polyaziridine compound according to any one of claims 1 to 15, and further comprising at least one additional component, wherein the amount of aziridine functional molecules having a molecular weight of less than 580 daltons, relative to the total weight of the crosslinker composition, is less than 5 wt.%, wherein the molecular weight is determined using LC-MS, and wherein the crosslinker composition contains less than 5 wt.% water.

39. Use of a polyethylenimine compound according to any of claims 1 to 34 or a crosslinker composition according to any of claims 35 to 38 for crosslinking a carboxylic acid functional polymer dissolved and/or dispersed in an aqueous medium.

40. A two-component system comprising a first component and a second component, each of which is independent and different from each other, and wherein the first component comprises a carboxylic acid functional polymer dissolved and/or dispersed in an aqueous medium, and the second component comprises a polyaziridine compound according to any of claims 1 to 34 or a crosslinker composition according to any of claims 35 to 38.

41. A substrate having a coating, said coating being obtained by: (i) Applying onto a substrate a coating composition obtained by mixing a first component and a second component of a two-component system, wherein the two-component system comprises a first component and a second component, each of the first and second components being separate and distinct from each other, and wherein the first component comprises a carboxylic acid functional polymer dissolved and/or dispersed in an aqueous medium, and the second component comprises a polyaziridine compound according to any of claims 1 to 34 or a crosslinker composition according to any of claims 35 to 38, and (ii) drying the coating composition by evaporation of volatiles.